CA1284602C - Low-temperature-effective detergent compositions and delivery systems therefor - Google Patents

Abstract

ABSTRACT

The invention provides novel low temperature mull compositions comprising at least one builder and a nonionic surfactant system with a pour point of less than about 75°F.
The mull compositions have a viscosity range between 10,000 and 100,000 centipoise and are stabilized by having a weight excess of builder to surfactant and/or by containing 0.1 to 5.0% by weight water. Adjuncts such as nonionic, anionic, cationic, and amphoteric surfactants; phase stabilizers;
fluorescent whitening agents; anti-redeposition agents;
corrosion-inhibiting agents; dyes; pigments; bleaches;
fabric softeners; enzymes; and fragrances may be added to the mull detergents. A novel delivery means is provided to deliver the detergent mull compositions into wash water.

Description

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DESCRIPTION

LOW-TEMPERATURE-EFFECTIVE DETERGENT COMPOSITIONS
AND DELIVERY SYSTEMS THEREFOR

TECHNICAL FIELD
The within disclosed invention relates to detergent mull compositions and delivery means therefor.
BACKGROUND OF THE INVENTION
It is well known to those skilled in the art that nonionic surfactants are useful in formulating laundry detergents for use in low water temperature washes. It is further known that nonionic surfactants are particularly efficient at removing oily soils from synthetic fabrics but that they are not as efficient at removing particulate soils as anionic surfactants. As a result it is desirable to include detergent builders in detergent formulations containing nonionic surfactants to improve performance on particulate soils and provide good overall cleaning performance. However, the amount of nonionic surfactant that can be included in powder detergents is limited by the amount that can be absorbed into or adsorbed onto the solid components. Agglomeration techniques usually produce dense particles that have little capacity for absorbing nonionic surfactants and the final compositions usually have poor solubility rates and flowability. Spray-drying techniques produce more porous particles that can absorb more nonionic surfactant. However, the temperatures involved in spray-drying can cause oxidation of the nonionic surfactant and it is desirable to add the nonionic surfactant in a second step if a high concentration is desired. Since the spray-drying process is energy and capital intensive, this approach results in high manufacturing costs. In addition, if certain builders are present, the spray-drying process itself can lead to the formation of insoluble particles that deposit on clothes during the washing process.

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High levels of nonionic surfactants can be readily incorporated into liquid laundry detergents. However, these formulations are normally severely limited in the type and amount of builder that can be incorporated therein since the builder must be soluble or dispersible in the formulation to prevent phase separation. As a result, the overall particulate soil removal performance of liquid laundry detergents is generally poorer than that of powder detergents.

U.S. Patent 4,316,812, issued to Hancock et al, appears to disclose liquid detergent compositions containing builders, a bleach, and a nonionic surfactant system, in which the solids have an average particle diameter of less than 10 microns and the nonionic surfactant system has a pour point of less than 10 C. However, it is expensive and inconvenient to use most conventional builders and most other solids at such a small particle size and a potential for the development of health and safety problems related to dusting with these builders and solids exists. Post milling the composition to reduce the particle size of the solids may eliminate the health and safety problems, but it requires an extra processing step that is energy intensive, and it generates significant heat which may affect temperature-sensitive compounds of the composition. Furthermore it may have a deleterious effect on encapsulated materials within the composition. Furthermore, no mention is made of the solubility characteristics of these formulations in cold water.

There have been attempts to combine high levels of nonionic surfactants and builders in laundry detergent formulations which have the physical form of mulls or pastes.
U.S. Patent 4,264,466, issued to Carleton et al, describes detergent mulls which contain ---------------------------~8460Z
chain structure clays to prevent phase separation of the liquid and solid components. U.S. Patent 4,409,136, issued to Chenq, discloses a paste detergent composition containing a specific nonionic surfactant along with a relatively high amount of water.

Because of the viscous nature of these paste formulations, it is difficult to deliver them into the washing machine from a conventional, liquid laundry detergent bottle, even one equipped with a pump dispenser. The use of a squeezable tube, similar to those used to dispense toothpaste, to dispense a liquid detergent in the form of a paste may be feasible from a technical consideration, but the size of the tube required to contain a reasonable amount of detergent for multiple wash loads would make it difficult for the consumer to use conveniently.

The use of pouches constructed of water soluble films to deliver unit dosages of laundry additives is well documented. However, there has been no demonstration in the prior art of the use of such pouches to contain and deliver a composition containing a high level of nonionic surfactant.
For example, U.S. Patent 4,115,292, issued to Richardson et al, shows compositions with low amounts of very high pour point nonionic surfactants and relatively high amounts of water in water-soluble polyvinyl alcohol pouches.

SUMMARY OF THE INVENTION

Because the steady rise in energy costs has made energy intensive manufacturing processes much less attractive, it is an object of this invention to provide detergent mull compositions containing high amounts of nonionic surfactants which are not produced by such energy consumptive processes.
Because there has been a trend in domestic laundry towards -------------------------------~--~~~~~~~~~~~~~~~~~~~

1'~84602 owered wash temperatures, it is a further object of this invention to provide detergent compositions in the form of mulls which have excellent solubility or dispersibility in cool and cold water and which efficiently remove both particulate and oily soils.

It is a still further object of this invention to provide detergent compositions in the form oE mulls which have excellent rates of dispersion/dissolution in cool and cold water and which have good phase stability without the addition of clays or other costly phase-stabilizing ingredients and without the requirement of an extremely small average particle size for the solid components of the mulls.

It is another object of this invention to provide a method for conveniently packing, storing and delivering these detergent compositions to washing machines.

In one embodiment, the invention provides novel low-temperature-effective detergent mull compositions comprising:
(a) a builder; and (b) a nonionic surfactant system, wherein the pour point of the system is preferably less than 75 F, more preferably less than 65 F and most preferably less than 40F; and wherein the average particle size of the solid components of the compositions is greater than 10 microns.

As will be more specifically discussed herein, the novel detergent mull compositions are rapidly soluble/dispersible in cold water and yet surprisingly provide good removal of oily and particulate soils from both natural and synthetic fibers, even though the HLB values of the surfactant systems of these compositions may be lower than is considered optimum for good detergency.

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~Z8~602 In a further embodiment, the invention provides novel low-temperature-effective detergent mull compositions comprising:
(a) a builder; and (b) a mixture of nonionic surfactants having pour points preferably less than 75F, more preferably less than 65 F, and most preferably less than 40 F;
wherein the compositions have an average viscosity of about 10,000 - 100,000 centipoise (cps) at 25C and at 6.25 revolutions per minute as measured on a Haake Rotoviscometer with an MVII sensor.

More preferably, the compositions of this embodiment have an average viscosity of about 20,000 - 60,000 cps and most preferably 30,000 - 50,000 cps under the same rheological test conditions.

In a still further embodiment, the invention provides a means for eliminating phase separation in these detergent mull compositions by adding about 0.1 to 5.0% by weight of the composition (unless otherwise specified, all further measures herein are by percent by weight of the composition) water to the detergent mull compositions of the prior embodiments.
This eliminates the need for the addition of more expensive materials, such as clays, and reduces the phase separation without significantly reducing the cold water solubility of the composition.

In yet another embodiment, the invention provides a premeasured, low-temperature-effective delivery system comprising:
a water soluble delivery pouch which contains a low-temperature-effective detergent mull which comprises:
(a) a builder; and (b) a nonionic surfactant system, wherein the pour point of the system is preferably less than 75 F, wherein the average particle size of the solid components of the mull is greater than 10 microns.

Furthermore, in any of the inventive detergent mull compositions or in the low temperature effective detergent delivery system described above, can be added further surfactants which do not render detergent solubility/dispersibility unacceptable, fluorescent whitening agents, bleaches, corrosion inhibiting agents, anti-redeposition agents, enzymes, dyes, pigments, fabric softeners, fragrances and other adjuncts.

The invention further provides a method of laundering fabrics by contacting the fabrics with the foregoing detergent mull compositions or with water into which the composition has been dissolved or dispersed, or by contacting the fabric with water to which the low temperature delivery system has been added.

DETAILED DESCRIPTION OF THE INVENTION

Recent studies have indicated that the average wash temperature of cold water washes in the United States is approximately 65 F but the temperature range of cold water washes is from about 90 F to about 40 F, and a significant number of wash loads is done in water with a temperature of less than 50 F. Surprisingly, many mull detergent compositions consisting predominantly of builders and cold water soluble nonionic surfactants will not dissolve/disperse at an adequate rate in cold water washes. It has been further surprisingly discovered that if the pour point of the nonionic surfactant system in these mulls is lower than the water temperature into which the mull is placed, the mull will dissolve/disperse at a rate sufficient to be acceptable for use as a consumer product. It is desirable to formulate these mulls with surfactant systems with pour points of less than about 75 F, more preferably less than about 65 F, and most preferably less than about 40 F to make them adequately soluble in most cold water washes.

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However, generally, as the pour point of the surfactantdecreases, so does its hydrophile-lipophile balance (HLB) value, and thus the pour points of the systems disclosed herein approach values much lower than is generally considered optimum for good 5 overall detergency. As disclosed in Schick, ~onionic Surfactants, Vol. 2, p. 607 (1962), optimal detergency was thought present at HLB values of around 13-15. HLB values are calculated from the number of ethylene oxide or other solubi]izing groups contained in the particular nonionic surfactant. Surprisingly, the 10 compositions disclosed in this invention nonetheless provide good detergency on both particulate and oily type soils even though the HLB values of these surfactant systems are quite low. In fact, some of the systems disclosed in this invention with the lowest HLB values provide the best overall detergency. There is no 15 disclosure or recognition in the prior art that the dispersion/
dissolution rates of these forms of detergents in cold water are highly dependent upon the pour points of the nonionic ~urfactant used in the formulations. Furthermore, no suggestion has been made in the prior art for conveniently delivering viscous 20 detergent compositions containing high levels of nonionic surfactant into the washing machine.

A further potential problem with mulls containing surfactants with low pour points is that the surfactants are too fluid at room temperature, and as a result, have more tendency to separate from 25 the solids in the mulls. This leads to phase separation upon storage of the detergent composition. It has been surprisingly found that the addition of very small amounts of water to the surfactant system will essentially eliminate phase separation in the final detergent mull composition. Water added in the range of 30 about 0.1 to 5.0%, based on the weight of composition, will adequately control phase separation without significantly reducing detergent solubility or dispersibility. Although not wishing to ~8460~
be bound to any one particular theory, applicants speculate that this effect results from flocculation of the solids in the mull which further increases their capacity to adsorb and absorb the surfactant. This is in contrast to the disclosure in U.S. Patent 5 4,264,466, which teaches the use of chain structure clays to prevent phase separation. These clays are more expensive to use than water and the formation of the chain structure in the mull will most probably reduce the rate of dissolution/dispersion of the resultant detergent composition in cool water.

The amounts of builders and surfactants that can be included in the formulations disclosed herein can vary considerably depending on the nature of the builders, the final desired viscosity and the amount of water added to the surfactant system.
In addition, other additives commonly found in detergent 15 compositions can also be included in the formulations described herein. These include but are not limited to further surfactants which do not render detergent dissolution/dispersion rates unacceptable, fluorescent whitening agents, bleaches, corrosion-inhibiting agents, anti-redeposition agents, enzymes, fabric 20 softeners, perfumes, dyes and pigments.

The amount of builder should be in the range of about 30 to 90% by weiqht of the total composition, with the surfactant system comprising about 10 to 70% by weight of the composition and the additional optional ingredients comprising about 0 to 60% by 25 weight of the composition. The ratio of these ingredients should be further adjusted along with the level of water, which increases the viscosity when added to the formulation, to provide a mull composition with a viscosity preferably in the range of about 10,000 to 100,000 centipoise (cps) at 25C and 6.25 revolutions 30 per minute as measured on a Haa~e Rotoviscometer with an MVII
sensor, and more pre,.erably in the range of about 20,000 to 60,000 cps and still lZ84602 more preferably in the range of about 30,000 to 50,000 cps.

Thus, the invention disclosed herein provides for mull detergent compositions that can be manufactured economically, will dissolve or disperse at acceptable rates in cool and cold water, have good overall cleaning performance and have controllable phase separation. The individual constituents of the novel compositions of this invention are described as follows:

NONIONIC SURFACTANT SYST~M

The surfactants of choice in the nonionic surfactant system have been selected from the nonionic surfactants including linear and branched, primary and secondary ethoxylated alcohols with an average chain length of 6 to 16 carbon atoms and averaging about 2 to 10 moles of ethylene oxide per mole of alcohol; linear and branched, primary and secondary ethoxylated, propoxylated alcohols with an average chain length of about 6 to 16 carbon atoms and averaging about 0 to 10 moles of ethylene oxide and about 1 to 10 moles of propylene oxide per mole of alcohol; linear and branched alkylphenoxy tpolyethoxy) alcohols, otherwise known as ethoxylated alkylphenols, with an average chain length of 8 to 16 carbon atoms and averaging 1.5 to 30 moles of ethylene oxide per mole of alcohol; and mixtures thereof.

Particularly preferred examples of these nonionic surfactants are those containing about 6 to 10 moles of ethylene oxide per mole of alcohol. While the invention encompasses branched chain nonionic surfactants, it is well known that for commercial purposes, linear nonionics are preferred due to their better biodegradability. Exemplary of such surfactants are the Neodol (trade ~ark of Shell Chemical Company) ethoxylate series. In particular, preferred surfactants include alcohol ethoxylates such ~'~8~60Z
a~ Neodol 91-6, which i5 a linear ethoxylated alcohol with a predominant chain length of about 9 to 11 carbons and averaging 6 moles of ethylene oxide per mole of alcohol, with a pour point of 45F; Neodol 91-8, having the same predominant carbon chain length 5 as Neodol 91-6 averaging 8.4 moles of ethylene oxide per mole of alcohol, with a pour point of 60F; Neodol 23-6.5, which is a linear ethoxylated alcohol with a predominant chain length of about 12 to 13 carbons averaging 6.5 moles of ethylene oxide per mole of alcohol, with a pour point of 60F: Neodol 25-7, which is 10 a linear ethoxylated alcohol with a predominant chain length of about 12 to 15 carbons averaging 7.2 moles of ethylene oxide per mole of alcohol, with a pour point of 70F; Neodol 25-9, having the same predominant chain length as Neodol 25-7, averaging 9 moles of ethylene oxide per mole of alcohol, with a pour point of 15 75F; and Neodol 45-7, which is a linear ethoxylated alcohol with a predominant chain length of about 14 to 15 carbons, averaging 7 moles of ethylene oxide per mole of alcohol, with a pour point of 70F. These particular alcohol ethoxylates are characterized by having HLB values ranging from 12.0 to about 14.0 and with 20 hydroxyl numbers (measured in milligrams of potassium hydroxide per gram) ranging from about 132-92.

Other nonionic surfactants may be selected from the Neodol ethoxylate series containing 1-5 moles of ethylene oxide per mole of alcohol. Exemplary of these particular surfactants are Neodol 25 91-2-5, which is a linear ethoxylated alcohol with a predominant chain length of about 9 to 11 carbons, averaging 2.5 moles of ethylene oxide per mole of alcohol, with a pour point of 5F, and an HLB value of about 8.1; and Neodol 25-3, which is a linear ethoxylated alcohol with a predominant chain length of 12 to 15 30 carbons, averaging 3 moles of ethylene oxide per mole of alcohol, with a pour point of 40 F, and an HLB value of about 7.9.

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Yet another particularly preferred surfactant is Surfonic*
JL-80X, which i9 an ethoxylated, propoxylated alcohol with an average chain length of 10 carbon atoms and averaging 9 moles of ethylene oxide and 1.5 moles of propylene oxide per mole of 5 alcohol, with a pour point of 15F, and an HLB value of about 13, available from Texaco Chemical Company.

Suitable alkylphenoxy (polyethoxy) alcohols, otherwise known as ethoxylated alkylphenols, include nonyl- and octylphenoxypoly (ethyleneoxy) alcohols, such as the Igepal*series manufactured by 10 GAF Corporation, e.g., Igepal*C0-210, a nonylphenol averaging 1.5 moles of ethylene oxide per mole of alcohol, and the Triton*
series, manufactured by Rohm and Haas Company, e.g., Triton"N-57, an ethoxylated nonylphenol averaging 5 moles of ethylene oxide per mole of alcohol.

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In general, the mulls of this invention have nonionic surfactant systems with pour points below about 75F, more preferably below about 65F, and most preferably below about 40F. Combinations of the these surfactants may be used in the detergent mulls of this invention. Preferred combinations include 20 those which combine a surfactant with a pour point of at least about 60 F with a surfactant with a much lower pour point such that the pour point of the combination is less than 75 F, more preferably less than 65F, and most preferably less than 40F. In practice, the pour point of combination~ of these 25 surfactants is usually between the pour points of each individual surfactant, but is not necessarily a weighted average of the pour points of each individual surfactant.

The predominant criterion for choosing the surfactants with particular pour points is the temperature of the cold water wash 30 into which the mulls of this invention will be placed.

*Trade Mark ~7~846~Z
Cold water wash temperatures in the United States vary greatly depending on both location and time of the year. As mentioned above, the average cold water wash has been determined to be about 65F. ~owever, the cold water wash temperatures can actually range from about 90 F to about 400F. The mulls of this invention are intended to be soluble in such wash temperatures.
Therefore, the pour points of the nonionic surfactant systems within the mulls should be at least lower, more preferably about 5F lower, most preferably about 10F lower than the temperature of the wash water into which they are placed.

BVILDERS

Suitable builders can be selected in this invention from the inorganic builders such as polyphosphates, orthophosphates, metaphosphates, tetraphosphates, tripolyphosphates, phosphates, pyrophosphates, carbonates, bicarbonates, borates, metasilicates, silicates, polysilicates, aluminosilicates (zeolites) and the alkali metal and ammonium salts of any of the foregoing. Further builders can be selected from such organic builders as nitrilotriacetic acid (NTA), polycarboxylates, polyhydroxy-sulfonates, citrates, succinates, oxydisuccinates, polyacrylicacid, ethylenediaminetetraacetic acid (EDTA) and the alkali metal and ammonium salts of the foregoing. Mixtures of any of the builders can be used. Two particularly preferred builders are sodium carbonate and sodium tripolyphosphate. An additional 25 preferred builder is sodium polysilicate manufactured by PQ
Corporation of Valley Forge, Pennsylvania, under the trademark Britesil ~

As previously mentioned, the combination of at least one builder and the nonionic surfactant system should be readily 30 soluble and/or dispersible in the wash water to which it is added. For the purposes of this invention, the concept of ~X8460Z

dispersibility includes solubility. For purposes of thisinvention, satisactory dispersibility is obtained when an observer is unable to visually discern any localized blue residue on fabrics washed with a mull composition containing a blue dye or 5 pigment, or in the washing machine in which these fabric~ were washed.

An additional concept which is relevant to the invention is rate of dissolution/dispersion. Over time, many solid particulates will disperse in water. However, to be acceptable 10 for use in this invention, the mulls should dissolve/disperse in water at about 65 F within at least about 25 minutes with gentle agitation, more preferably within about 15 minutes, and most preferably within about 10 minutes.

The particle size of the builders i9 not critical if the 15 viscosity of the composition is adjusted to be in the range of about 10,000 to 100,000 centipoise. As a result, the builder used in this composition can thus be generally used as received from the supplier without an extra processing step to mill the particles to a desired size as required in U.S. Patent 4,316,812.

Further, if the viscosity of the composition is maintained in the appropriate range, no dispersant is required to prevent the builders from separating from the balance of the compositions of this invention. Although U.S. 4,316,812 contends no dispersant is needed for its liquid detergent, in fact, all of its examples 25 include finely divided silica ("Aerosil"~, polyethylene glycol, or a combination of the two as dispersants (cf. Column 4, lines 3-7 and Example 5, column 5, line 54, showing use of polyethylene glycol).

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The average particle size of the solid components of the mull compositions of this invention is preferably between 10 to 500 microns, more preferably about 50 to 250 microns, and most preferably about 50 to 175 microns. The average particle size of 5 one of the preferred builders, sodium tripolyphosphate (STPP) --which, in the Examples following, constitutes a major portion of the solids in the mull compositions -- was determined by screening and is set forth below in Table I:

TABLE I
Average Particle Size of STPP

Percent by Weight _~ Part. Size (microns) 34 ~ 75 0.5 >400 As noted above, particle size, however, is not critical, but the amounts of builder, surfactants and water must be adjusted to 20 provide satisfactory viscosity. In the invention, the viscosity is in the range of preferably about 10,000 to 100,000 centipoise (cps) at 25C and at 6.25 revolutions per minute (rpm) as measured with a Haake Rotoviscometer with an MVII sensor, more preferably about 20,000 to 60,000 cps.

In order to meet the desirable criteria outlined above, the inventive mull compositions comprise preferably about 30 to 90% by weight of at least one builder, about 10 to 70% by weight surfactant system, and about 0 to 60% by weight adjuncts (as described below); more preferably about 40 to 80% by weight of at 30 least one builder, about 20 to 60% by weight surfactant system, and about 0 to 40% by weight adjuncts; and most preferably about 50 to 75% by weight of ~346~Z
at least one builder, about 25 to 50% by weight surfactant system, and about 0 to 25% by weight adjuncts.

PHASE STABILIZER

Water has been used in Examples 12-14 below a~ a phase 5 stabilizer and for viscosity control. In fact, in these particular uses, a clay or other thickener is not utilized. While it is not entirely understood why water may act as a thickener in this invention, it is believed that it may cause floccula~ion of the solids in the compositions of thi~ invention which leads to further 10 adsorption or absorption of the surfactants. The amount of water required to produce the desired viscosity and adequate phase stability appears to show a critical range. This amount ranges from about 0.1% to about 5%, more preferably 0.4% to about 2% by weight of the composition. Furthermore, deionized water is 15 especially preferred for use, although from a commercial standpoint, tap water appears acceptable.

FLUORESCENT WHITENING AGENT

In the invention, fluorescent whitening agents, or brighteners, are preferably added to improve whitening of fabrics. Such 20 fluorescent brighteners can be selected from stilbene brighteners, and their derivatives: styrylnaphthalene brighteners and their derivatives and styrene brighteners and their derivatives.
Exemplary of the derivatives used is the preferred brightener Tinopal ~ 5BM-XC, produced by Ciba-Geigy A.G., Switzerland.
25 Other brighteners include those disclosed in U.K. patents 1,298,577, 2,076,011, 2,026,054, 2,026,566, 1,393,042; and U. S.
patents 3,951,960, 4,298,290, 3,993,659, 3,980,713 and 3,627,758.

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OPTIONAL SURFACTANTS

Further nonionic, anionic, cationic and amphoteric surfactants may be combined with the detergent mulls of this invention in a manner to impart greater cleaning where desired, with the proviso that such added surfactants do not render detergent solubility or dispersibility unacceptable, especially in cool or cold water (<75 F).

For example, anionic surfactants may be added to increase cleaning of particulate soils. Suitable examples of such anionic surfactants include the ammonium, substituted ammonium (e.g., mono-, di-, and triethanolammonium), alkali metal, and alkaline earth metal salts of C6-C20 fatty acids and rosin acids, linear and branched alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, alkanesulfonates, olefin sulfonates, hydroxyalkane-sulfonates, fatty acid monoglyceride sulfates, alkyl glyceryl ether sulfates, acyl sarcosinates, and acyl N-methyl taurides.
Further, suitable nonionic surfactants include polyoxyethylene carboxylic acid esters, fatty acid glycerol esters, fatty acid and ethoxylated fatty acid alkanolamides, certain block copolymers of propylene oxide and ethylene oxide, and block polymers of propylene oxide and ethylene oxide with propoxylated ethylenediamine. Also included are such semi-polar nonionic surfactants like amine oxides, phosphine oxides, sulfoxides, and their ethoxylated derivatives.
Suitable cationic surfactants include the quaternary ammonium compounds in which typically one of the groups linked to the nitrogen atom is a Cl2-Cl8 alkyl group and the other three groups are short-chain alkyl groups which may bear inert substituents such as phenyl groups.

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Further, suitable amphoteric and zwitterionic surfactants which contain an anionic water-solubilizing group, a cationic group, and a hydrophobic organic group include aminocarboxylic acids and their salts, iminodicarboxylic acids and their salts, alkylbetaines, alkylamidopropylbetaines, sulfobetaines, alkylimidazolinium derivatives, certain quaternary ammonium compounds, certain quarternary phosp~lonium compounds and certain tertiary sulfonium compounds. Other examples of suitable zwitterionic surfactants can be found described in U.S. Patent 4,005,029, issued to Jones, at Columns 11-15.

Further examples of anionic, nonionic, cationic and amphoteric surfactants which may be suitable for use in this invention are depicted in Kirk-Othmer, EncvcloPedia of Chemical Technoloay, Third Edition, Vol. 22, pages 347-387, and McCutcheon's Deterqents and Emulsifiers, North American Edition, 1983.

FURTHER AWUNCTS
Further cleaning adjuncts can include enzymes.
Particularly preferred are amylases and proteases.
Particularly preferred are proteases such as alkaline proteases, also denoted as subtilisins. Suitable examples include SavinaseX, AlcalaseX, and EsperaseX, all from Novo Industri A/S, Denmark, and Maxacal~ and MaxataseY from Gist Brocades, N.V., Netherlands.

Bleaches can also be added to the compositions of this invention, preferably peroxygen bleaches such as percarbonate, perborate, and the salts thereof, e.g., sodium perborate monohydrate, and organic and inorganic peroxy compounds, such as peracids, e.g., perlauric acid, and potassium peroxymonosulfate (available from E.I. Du Pont de Nemours, Delaware, under the trade mark Oxone~. Additionally, bleach activators can be ----------------------------------------", j :i ~.~8~602t incorporated , such as tetraacetylethylenediamine (TAED), ketonesor aldehydes.

Yet other common detergent additives can be included in the formulas of this invention, such as dyes, pigments and colorants, 5 exemplary of which are ultramarine blue (UMB) pigments, anthraquinone dyes, and Monastral dyes, which are manufactured by E.I. DuPont du Nemours, Dela~i~re. Especially preferred is UMB to impart a pleasing color to the mull composition aR well as to deliver a bluing effect on fabrics. Fabric softeners may be added 10 to the inventive mulls. These fabric softeners are generally quaternary ammonium compounds and their salts, as disclosed in U.S.
Patents 4,250,043, issued to Jones, and 4,339,335, issued to Wixon.

Use of such fabric softeners is particularly favored in the mulls of this invention due to the general absence of anionic surfactants in the mulls' formulations, Further, fragrances of various sorts, most of which are ketones or aldehydes containing substituted phenyl rings, can be added to the mulls. Also, corrosion-inhibition agents and anti-redeposition agents may be 20included in these mulls.

DELIVERY FILMS

As noted in the foregoing, because of the physical nature of the mull detergent compositions, packaging and delivery of these compositions into the wash water cannot be implemented efficiently 25 by most current commercial detergent packaging systems. As a result another preferred embodiment of this invention comprises a delivery system comprising (~) a water-soluble delivery pouch, which comprises a film prepared from at least one film-forming polymer and (b) an effective amount of a low temperature detergent 30 mull which comprises a nonionic surfactant system and a builder.

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Particularly preferred films are castable, water-soluble films comprised of polyvinyl alcohols which have number average molecular weights from about 5,000 - 250,000. These polyvinyl alcohols generally have about 1 to 25% residual acetate groups, more preferably 5 to 20~ residual acetate groups, and most preferably about 10 to 15% residual acetate groups. Additionally, such polymers as polyvinyl pyrrolidone, methyl cellulose, polyethylene oxide, gelatin and other film formers can be utilized.
Plasticizers such as trimethylolpropane, glycerol, polyethylene glycol and others known to those skilled in the art can be included in the film to provide the film strength and flexibility required for producing, filling, shipping and storing the pouches prepared from these films. In addition other ingredients such as wetting agents, defoamers, and anti-blocking agents can be included in these films to aid in their manufacture and in the preparation of pouches made from these films.

The films included in this embodiment can have a thickness of from 1.0-5.0 mils, with the thickness and film material being selected to provide the optimum balance of film strength and cold water solubility. It has been found that films with a thickness of 1.5-3.5 mils produced from polyvinyl alcohol with about 12%
residual acetate groups are preferred for this particular embodiment of the invention.

It has been further found that when pouches are produced from these preferred films and stored in contact with the detergent mulls of this invention, significant losses of impact strength can occur. It has been found however, that the incorporation of small amounts of known film plasticizers into the detergent mull composition itself surprisingly minimizes this loss of impact strength of the films after storage in contact with the detergent compositions. Thus, a further embodiment of this invention lZ8460X
comprises a delivery system comprising (a) a water-soluble delivery pouch, and (b) an effective amount of a low-temperature-effective detergent mull which comprises a builder, a nonionic surfactant system and 30~ or less, based on the weight of the surfactant 5 system, of at least one ingredient that is suitable for use as a film plasticizer for the film used to form the water-soluble pouch.

This invention is further exemplified by the examples set forth below which are intended to illustrate but not restrict the scope of the invention.

The following detergent formula was used to prepare the mull detergent compositions in Examples 1-10:

1;;~84~

INGREDIENT % BY WEIGHT
-Nonionic Surfactantl 30.0 Sodium Tripolyphosphate2 55.4 Sodium Carbonate 10.5 Britesil ~ C-243 ].5 Alcalase ~ 2.oT4 0.7 Savinase ~ 8.os4 0~7 Tinopal ~ 5BM-XC5 o.g UMB Pigment 0.1 Fragrance 0.2 1 Disclosed in TABLE II, below.
2 Builders.

3 Polysilicate builder with an SiO2/Na20 ratio of 2.4:1, manufactured by PQ Corporation of Valley Forge, Pennsylvania.

4 Proteolytic enzymes, manufactured by Novo Industri A/S, Denmark.

5 Fluorescent whitening agent, manufactured by Ciba Geigy A.G., Switzerland.

6 Ultramarine Blue.

Approximately 2 kilograms of each of the 10 exemplified compositions in TABLE II were prepared by premixing the nonionic surfactants together and then mixing the surfactant system together with the remainder of the ingredients in a Hobart mixer.
~elatively low shear mixing was used and a total mixing time of 15-30 minutes was sufficient to provide uniform distribution of the ingredients in the resulting mulls. The pour point of each surfactant mixture was measured using the basic procedure found in ASTM D97-66. After each composition was prepared, approximately 30 grams of each were placed in individual pouches prepared from ~Z8460Z
Quiksol*A film supplied by Polymer Films Inc. of Rockville, Conn. The films were 1.5 mils thick and were composed of polyvinyl alcohol with an average molecular weight of about 96,000 and approximately 12% residual acetate groups. The mulls were 5 enclosed in the films, which were heat sealed. The resulting pouches were then placed at 40 F for 24-48 hours (to simulate storage by the consumer, such as in a garage), removed and their solubility in 40F water was evaluated. This procedure involved placing the pouches in a washing machine containing 68 liters of 10 water at 40F, and initiating a wash cycle using the "delicate"
setting to control agitation. After ten minutes, the agitation was terminated, and the machine was drained and inspected for residual detergent. Residual detergent is determined by whether any residue remains which is visually discernible in the washing 15 machine. This is a measure of the dissolutiontdispersion rates of the mull compositions. The results are shown in TABLE II, below.

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~'~8460%
Reviewing TABLE II, one can see that the composition of Example 1, which contains two surfactants, Neodol 23-6.5 and Neodol 25-9, which are considered to be water soluble by their manufacturer, failed to completely dissolve at 40F under the test conditions. In addition when this composition was stored at 70 F and added to wash water at 63F, it again failed to completely dissolve under the test conditions described previously. Example 4, by comparison, which contains Neodol 91-2.5, dissolved/dispersed completely in the cold (40 F) water even after storage at 40 F. This was particularly surprising since this particular surfactant is considered by its manufacturer to be less soluble in water than both of the surfactants used in Example 1. Thus, surprisingly, adding a surfactant system that is apparently less soluble in water to the remaining components of Examples 1-10 improved the dissolution/dispersion rates of the mull compositions in cold water.

Further examination of Table II shows that Examples 4, 6, 9 and 10, with surfactant systems with pour points less than or equal to about 36 F completely dissolved/dispersed in 40 F
water under the test conditions described above. Thus, the applicants have concluded that the dissolution/dispersion rates of the mulls of this invention are related to the pour points of the surfactant systems in these mulls and that the pour points should be at least lower than the temperature of the water in which the mulls are placed to provide acceptable dissolution/dispersion rates in the water. Apparently, the examples which have the lower pour point surfactant systems maintain more fluidity in cold water, which facilitates their dispersion. It is surprising that these differences in fluidity of already viscous samples are more important than overall water solubility in controlling the rates of dissolution/dispersion of these compositions in cold water.

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Performance studies on cotton, cotton/polyester blends, and polyester fabrics soiled with a synthetic sebum or a synthetic clay soil (Performance Test I) show that reducing the pour point of the surfactant system does not reduce the cleaning efficacy of these composition-~ even if the HLB value is reduced to a level much lower than that normally prescribed for good detergency.
Thus, the compositions of this invention provide good cleaning as well as good solubility/dispersibility characteristics. The cleaning performance was evaluated by washing swatches treated with these soils in water at 100F containing 100 ppm water hardness (as CaCO3) with a molar ratio of Ca2 :Mg2 of 3:1 and a concentration of 0.08% of the appropriate detergent mull composition in a commercial washing machine. The reflectance values of the swatches were measured before and after washing, and the Kubelka-Mun'; equation was used to calculate % soil removal.

PERFORMANCE TEST I
EXAMPLE HLB % SOIL REMOVAL
COTTON POLYCOTTON POLYESTER
SEBUM CLAY SEBUM CLAY SEBUM CLAY
1 12.687.486.7 79.9 99.5B2.1 99.2 6 10.389.189.5 80.6 99.685.6 99.5 9 12.988.689.1 73.1 99.081.5 99.4 11.989.690.2 78.2 10086.7 100 LSD 1 2.6 3.1 4.1 1.5 2.9 0.5 , 1 LSD is at 90~ confidence level.

It was particularly surprising that Examples 6 and 10 performed so well, ~ince they each contain a significant amount of Neodol 91-2.5, which is not merely considered insoluble by its manufacturer but unsuitable for 1~8460Z
for good detergency as well. Further surprising results were obtained with Example 10. Example 10 is a ternary system containing mixtures of three nonionic surfactants, two of which have very low pour points tNeodol*91 2.5 and Surfonic JL-80X). On 5 two fabrics, cotton and polyester, this ternary system had significantly better particulate (clay) soil removal, than the composition of Example 1, which was unexpected based on the HLB's of the surfactant systems.

PERFORMANCE TEST II
Selected examples based on the compositions of TABLE II were tested for performance at 40F, under the same conditions as the foregoing, except for temperature and the use of only cotton and polyester fabrics. The results for ~ soil removal of both sebum (oily) and clay (particulate) soils are shown below:
SURFACTANT HLB FABRIC ~ SOIL REMOVAL

SEBUM CLAY

Neodol 23-6.51 12.0 Cotton 75.2 83.9 Neodol 91-2.5/ 10.3 " 82.1 83.2 Neodol 23-6.51 12,0 Polyester 84.1 96.8 Neodol 91-2.5/2 10.3 " 90.7 96.4 LSD3 3.9 2.3 1 100~ of this surfactant was used.
50%t50~ mixture of these surfactants was used.

3 LSD is at 90~ confidence level.
Mulls were predissolved in the water before tests were initiated.
*Trade Marks -27-1~8460Z

The above results show that a combination of nonionic surfactants having a reduced pour point and reduced HLB values surprisingly demonstrated soil removal properties in a low temperature wash as good as or better than a single nonionic surfactant which one would expect to have better solubility and detergency than the combination.

50 kilogram quantities of mull detergent compositions were prepared using a ribbon blender and the formulas are ~ummarized below. In Example 12, the water wa8 added to the surfactant system before this system was mixed with the rest of the composition.

% %

15 Neodol*23-6.5 3 7 Surfonic JL-80X 26.3 26.1 Deionized Water -- 0.6 Sodium Tripolyphosphate 55.4 55.0 Sodium Carbonate 1~.5 10.5 20 Britesil ~ C-24 1.5 1.5 Alcalase ~ 2.0T 0.8 0.8 Savinase ~ 8.0S 0.6 0.6 Tinopal ~ 5BM-XC 0.9 0,9 Pigment 0.1 0.1 25 Fragrance 0.2 0.2 The composition of Example ll was observed to have phase *Trade Marks ~Z8460Z

separation after storage at room temperature. The separation was quantified by placing 1000 grams of the composition in a one-liter graduated cylinder for one week at room temperature and then removing and weighing the separated liquid phase that appeared on top of the remainder of the composition. It was found that the weight of the liquid totaled 4.8% of the total composition. When the detergent of composition 12 was evaluated under the same conditions, 0.1~ or less liquid phase separation was observed.

Furthermore, 2 kilogram quantities of the detergent composition in Example 12 were prepared and tested for solubility as were Examples 1-10. The composition of Example 12 dissolved/
dispersed completely in less than ten minutes in 40F water.

2 kilogram quantities of mull detergent compositions were prepared using a Hobart mixer and their formulas are summarized below. Approximately 25 grams of each composition were placed in a 2 x 3 inch water-soluble pouch constructed from a 2.5 mil thick film comprised predominately of polyvinyl alcohol (number average molecular weight of about 10,000 and about 12~ residual acetate groups) with 5% glycerol and 4% trimethylolpropane as plasticizers. The pouches were stored for nine weeks at 70F/50% relative humidity.

1~8460X

Neodol 23-6.5 3.7 3.6 Surfonic JL-80X 26.1 25.6 5 Deionized Water 0.6 0.6 Sodium Tripolyphosphate ' 55.0 54.0 Sodium Carbonate 10,5 10.3 Britesil ~ C-24 1.5 1.5 Alcalase ~ 2.OT 0.8 0.8 lO Savinase ~ 8.0S 0.6 0.6 Tinopal ~ 5BM-XC 0.9 0.9 Pigment 0.1 0.1 Fragrance 0.2 0.2 Glycerol -- 0.9 15 Trimethylolpropane -- 0.9 *Trade Marks After nine weeks of storage, the film from the pouches containing the composition of Example 13 was obviously brittle while the film from the pouches containing the composition of Example 14 was much more flexible. Impact strength measurements made on these films using a Rheos Total Energy Impact Strength Tester and testing conditions of 35F/42% relative humidity indicate that the films used with the composition in Example 14 had about five times more impact strength than the films used with the composition in Example 13. As previously discussed, this shows that the addition of plasticizer directly to the mull minimizes the loss of film impact strength when the film is exposed to the mull. This was unexpected and further shows the unobvious characteristics of the delivery system of this invention.

The invention i5 further illustrated by reference to the claims which follow below.

Claims (36)

1. A low-temperature-effective detergent mull composition comprising:
(a) at least one builder; and (b) a nonionic surfactant system, wherein the pour point of the system is less than about 24°C (75°F); and wherein the viscosity of the mull composition ranges from about 10,000 to 100,000 centipoise;
wherein the mull composition is rendered stable by the presence of (i) a weight amount excess of builder with respect to surfactant; (ii) 0.1 to 5.0% by weight water as a phase stabilizer; or (iii) both (i) and (ii).

2. The mull composition of Claim 1 wherein the particle size of the solid components of the mull composition exceeds about 10 microns.

3. The mull of claim 1 wherein in (a), at least one builder is selected from the group consisting essentially of:
polyphosphates, orthophosphates, metaphosphates, tripolyphosphates, phosphates, pyrophosphates, carbonates, bicarbonates, borates, silicates, polysilicates, aluminosilicates, metasilicates, and the alkali metal and ammonium salts of any of the foregoing; nitrilotriacetic acid, polycarboxylates, polyhydroxy sulfonates, citrates, succinates, oxydisuccinates, polyacrylic acid, ethylenediaminetetraacetic acid, and the alkali metal and ammonium salts of any of the foregoing; and mixtures thereof.

4. The mull of Claim 1 wherein the surfactant system further comprises at least one nonionic surfactant selected from the group consisting essentially of:
linear and branched, primary and secondary ethoxylated alcohols with an average chain length of 6 to 16 carbon atoms and averaging about 2 to 10 moles of ethylene oxide per mole of alcohol; linear and branched, primary and secondary ethoxylated, propoxylated alcohols with an average chain length of about 6 to 16 carbon atoms and averaging about 0 to 10 moles of ethylene oxide and about 1 to 10 moles of propylene oxide per mole of alcohol; linear and branched alkylphenoxy (polyethoxy) alcohols with an average chain length of 8 to 16 carbon atoms and averaging 1.5 to 30 moles of ethylene oxide per mole of alcohol; and mixtures thereof.

5. The mull of Claim 1 further comprising (e) at least one adjunct selected from the group consisting essentially of:
nonionic, anionic, cationic, and amphoteric surfactants;
phase stabilizers; fluorescent whitening agents; anti-redeposition agents; corrosion-inhibiting agents; bleaches; dyes; pigments;
enzymes; fabric softeners; and fragrances.

6. The mull of Claim 5 wherein the phase stabilizer is water.

7. The mull composition of Claim 1 wherein the pour point of the system is less than about 65°F and the average particle size of the solid components of the mull composition is about 50 to 250 microns.

8. The mull of Claim 5 wherein the fluorescent whitening agents include stilbene, styrylnaphthalene and styrene brighteners and their derivatives.

9. The mull of Claim 5 wherein the pigment is ultramarine blue.

10. The mull of Claim 5 wherein the enzymes include amylases and proteases.

11. The mull of Claim 5 wherein the builder of (a) is about 30% to 90% by weight, the surfactant system of (b) is about 10% to 70% by weight, and the adjunct of (c) is about 0% to 60% by weight, of the mull.

12. The mull of Claim 11 wherein the pour point of the surfactant system is less than about 65°F.

13. The mull of claim 11 wherein the pour point of the surfactant system is less than about 40°F.

14. The mull of claim 11 wherein the surfactant system comprises at least two nonionic surfactants, one of which has a pour point of less than about 40°F.

15. The mull of claim 11 wherein the surfactant system comprises three nonionic surfactants, two of which have pour points of less than about 40°F.

16. The mull of claim 11 wherein the surfactant system has a pour point of at least about 5°F less than the water in which the mull is used.

17. A low temperature effective detergent delivery system comprising:
a water soluble pouch containing a detergent mull which comprises:
(a) at least one builder; and (b) a nonionic surfactant system having a pour point less than about 75°F;
wherein the mull has a viscosity between about 10,000 and 100,000 centipoise;
wherein the mull composition is rendered stable by the presence of (i) a weight amount excess of builder with respect to surfactant; (ii) 0.1 to 5.0% by weight water as a phase stabilizer; or (iii) both (i) and (ii).

18. The delivery system of Claim 17 wherein the delivery pouch comprises a film which is prepared from at least one castable film-forming polymer selected from the group consisting essentially of:
polyvinyl alcohol, polyvinyl pyrrolidone, methyl cellulose, polyethylene oxide, gelatin and mixtures thereof.

19. The delivery system of Claim 18 wherein the polymer is a polyvinyl alcohol with a number average molecular weight of about 5,000 to 250,000 and about 1-25% residual acetate groups.

20. The delivery system of Claim 19 wherein the film contains at least one plasticizer.

21. The delivery system of claim 17 wherein in (a), at least one builder is selected from the group consisting essentially of:
polyphosphates, orthophosphates, metaphosphates, tripolyphosphates, phosphates, pyrophosphates, carbonates, bicarbonates, borates, silicates, polysilicates, aluminosilicates, metasilicates, and the alkali metal and ammonium salts of any of the foregoing; nitrilotriacetic acid, polycarboxylates, polyhydroxy sulfonates, citrates, succinates, oxydisuccinates, polyacrylic acid, ethylenediaminetetraacetic acid, and the alkali metal and ammonium salts of any of the foregoing; and mixtures thereof.

22. The delivery system of Claim 17 wherein the surfactant system of (b) further comprises at least one nonionic surfactant selected from the group consisting essentially of:
linear and branched, primary and secondary ethoxylated alcohols with an average chain length of 6 to 16 carbon atoms and averaging about 2 to 10 moles of ethylene oxide per mole of alcohol; linear and branched, primary and secondary ethoxylated, propoxylated alcohols with an average chain length of about 6 to 16 carbon atoms and averaging about 0 to 10 moles of ethylene oxide and about 1 to 10 moles of propylene oxide per mole of alcohol: linear and branched alkylphenoxy (polyethoxy) alcohols with an average chain length of 8 to 16 carbon atoms and averaging 1.5 to 30 moles of ethylene oxide per mole of alcohol; and mixtures thereof.

23. The delivery system of Claim 17 further comprising (c) at least one adjunct selected from the group consisting essentially of:
nonionic, anionic, cationic, and amphoteric surfactants;
phase stabilizers; fluorescent whitening agents; anti-redeposition agents; corrosion-inhibiting agents; bleaches; dyes; pigments;
fabric softeners; enzymes; and fragrances.

24. The delivery system of Claim 23 wherein the phase stabilizer is water.

25. The delivery system of Claim 23 wherein the fluorescent whitening agents include stilbene, styrylnaphthalene and styrene brighteners and their derivatives.

26. The delivery system of Claim 23 wherein the pigment is ultramarine blue.

27. The delivery system of Claim 23 wherein the enzymes include amylases and proteases.

28. The delivery system of Claim 23 wherein the builder of (a) is about 30% to 90% by weight, the surfactant system of (b) is about 10% to 70% by weight, and the adjunct of (c) is about 0% to 60% by weight, of the mull.

29. The delivery system of Claim 28 wherein the pour point of the surfactant system is less than about 65°F.

30. The delivery system of claim 28 wherein the pour point of the surfactant system is less than about 40°F.

31. The delivery system of claim 28 wherein the surfactant system comprises at least two nonionic surfactants, one of which has a pour point of less than about 40°F.

32. The delivery system of claim 28 wherein the surfactant system comprises at least three nonionic surfactants, two of which have pour points of less than about 40°F.

33. The delivery system of claim 28 wherein the surfactant system has a pour point of about 5°F less than the water in which the mull is used.

34. The delivery system of claim 28 wherein the mull further comprises (d) at least one film plasticizer in an amount of no more than about 30% by weight of the surfactant system.

35. A method for laundering fabrics comprising:
contacting the fabrics with a low-temperature-effective detergent mull which comprises:
(a) at least one builder; and (b) a nonionic surfactant system;
wherein the viscosity of the mull composition ranges from about 10,000 to 100,000 centipoise;
wherein the mull composition is rendered stable by the presence of (i) a weight amount excess of builder with respect to surfactant; (ii) 0.1 to 5.0% by weight water as a phase stabilizer; or (iii) both (i) and (ii).

36. A method for laundering fabrics comprising:
contacting the fabrics with wash water into which has been dispersed a premeasured, low-temperature-effective delivery system comprising:
a water soluble delivery pouch containing a detergent mull which comprises:
(a) at least one builder; and (b) a nonionic surfactant system wherein the pour point of the system is less than about 75°F, and wherein the viscosity of the mull ranges from about 10,000 to about 100,000 centipoise;
wherein the mull composition is rendered stable by the presence of (i) a weight amount excess of builder with respect to surfactant; (ii) 0.1 to 5.0% by weight water as a phase stabilizer; or (iii) both (i) and (ii).