MXPA06006253A - Automatic machine laundering of fabrics - Google Patents

Abstract

The invention provides a method of laundering fabrics in an automatic washing machine having a drum wherein the automatic washing machine is operated so as to cause it to run through at least one wash cycle and at least one rinse cycle. Such a method comprises:(a) during the at least one wash cycle forming in the drum an aqueous washing liquor containing a detersive surfactant component and a detergent builder component, the aqueous wash liquor having pH above about 7;(b) contacting fabrics to be laundered with the aqueous wash liquor in the drum;(c) during the rinse cycle forming in the drum an aqueous rinse liquor and contacting the fabrics with the rinse liquor;(d) adding to the rinse liquor sufficient acid source to bring the pH of the rinse liquor in the range of from about 4 to about 7, preferably from about 4.5 to about 6.5. The use of this lowered pH in the rinse liquor gives a variety of cleaning benefits, and preferably fabric care benefits in combination with rinse additive, in the context of an automatic washing process. The invention also provides particular systems for application of the acid source to the rinse liquor.

Description

WASHING OF FABRICS IN AUTOMATIC WASHING MACHINE FIELD OF THE INVENTION This invention relates to methods for washing fabrics in an automatic washing machine in a cycle having a wash cycle, a rinse cycle and preferably a spin cycle between the wash cycle and the rinse cycle. It also refers to systems that can be used to add washing and rinsing additives in this washing process.

BACKGROUND OF THE INVENTION The washing of fabrics in automatic washing machines is well known.

A normal automatic washing machine washing operation includes at least one wash cycle (and in some cases more than one wash cycle), a spin cycle that removes significant proportions of wash solution from the wash cycle and a final cycle of rinsing. Cleaning agents such as surfactants and detergent additives are usually added to the drum of the washing machine in the wash cycle to aid in the mechanical removal of dirt and fabric stains. It is also known to add additional materials, in particular fabric care agents such as fabric softeners, touch modifiers and anti-wrinkle agents, during the rinsing cycle and not during the washing cycle, to avoid interference of other components present in the washing solution during previous stages of the washing operation. It is required that some of these materials be deposited on the fabric to provide maximum benefit. This applies, for example, to perfumes, polishing agents, beneficial agents for the care of the fabric and agents for releasing dirt. It would be desirable to maximize the deposition potential of these materials on the fabric when they are added to the rinse cycle. The pH of the aqueous wash solution during the wash cycle is generally high, in particular above 7 and more commonly at least 9, often in the range of 10.5 to 12.5, and sometimes higher.

Due to the different nature of the additives commonly included in the rinse cycle and the removal of most of the wash solution, the pH of the rinse solution is generally lower than in the wash cycle but is usually not below 7. Rinsing clothes with a solution or rinse bath that has a pH below 7 is known, but this has not been done in the context of automatic washing processes. Washing processes with automatic washing machines have special requirements since it is usual to include a complex detergent composition in the washing cycle and it is common to include a variety of types of fabrics in a single wash. In particular, manufacturers of fabric washing compositions constantly strive to improve the properties of these compositions while retaining a composition that is technical and Economically attractive In particular, the removal of greasy stains and the removal of bleaching stains is an aspect that generally requires improvement, but the types of components of a laundry composition that improve this performance tend to be one of the components more expensive, such as bleaching components. Therefore, it would be desirable to provide a means by which these problems could be solved without the need to increase the level of costly components. A problem that occurs with washing processes in automatic washing machines is the gradual deposit of waste in the laundry during many washings. This residue can lead to the gradual dulling of dark colored fabrics or, in general, produce a "lackluster" appearance on white or other light fabrics. It also makes it more difficult to remove stains from the surface of the fabric on which the residue has been deposited. Again, it would be desirable to provide methods for treating these problems without necessarily requiring expensive components in the laundry composition.

BRIEF DESCRIPTION OF THE INVENTION In accordance with this invention a method is provided for washing fabrics in an automatic washing machine that has a drum, operating the automatic washing machine to cause it to work at through at least one wash cycle and at least one rinse cycle; The method comprises: (a) During the at least one wash cycle, forming an aqueous wash solution containing a detersive surfactant component and a detergent additive component in the drum, the aqueous wash solution has a pH greater than 7.; (b) contacting the fabrics to be washed with the aqueous wash solution in the drum; (c) during the rinse cycle, form an aqueous rinse solution in the drum and contact the fabrics with the rinse solution; (d) adding to the rinse solution sufficient acid source to bring the pH of the rinse solution to a range from about 4 to about 7, preferably from about 4.5 to about 6.5. For the first time, an automatic washing machine washing method is provided in which the pH of the rinse solution is brought to the range of 4 to 7, preferably 4.5 to 6.5. It has been found that this provides a wide variety of benefits in combination with a number of different rinse additives, as discussed hereinafter. It has also been found that the use of a low pH rinse solution has, by itself, particular benefits in the context of automatic washing processes, even if no additive is included.

Rinse in the rinse cycle. Accordingly, in accordance with a second aspect of this invention, the use of a pH of from about 4 to about 7, preferably from about 4.5 to about 6.5, in the rinse cycle of an automatic washing machine washing process is provided. improve the discoloration of the bleach stains and / or promote the removal of grease and / or promote the cleaning of complex soils, and / or reduce the transfer of the colorant and / or reduce the accumulation of residues on the fabrics. In this context, "dirty complexes" are accumulated combinations of body dirt, detergent, softener and / or hard water residues. The type of waste whose accumulation is reduced is believed to contain calcium and is related to washing in hard water. In a third aspect, there is provided a system for providing the sequential addition of washing additives and rinsing additives to the washing and rinsing cycles, respectively, of a fabric washing operation carried out in an automatic washing machine containing a drum. . This system comprises: (a) A unit dose package comprising at least one compartment containing washing additive material comprising a detersive surfactant component and a detergent additive component; said wash additive material serves to provide an aqueous wash solution having a pH greater than 7; and at least one additional compartment containing an acid source to bring the pH of the rinse solution formed during said rinse cycle to a pH of from about 4 to about 7, preferably from about 4.5 to about 6.5; (b) a rigid receiver structure within which at least the rinsing additive compartment or compartments of said unit dose package can be inserted at the beginning of the washing operation; said receiving structure is placed inside the drum of said automatic washing machine in a location that puts it in significant contact with the washing and rinsing water during the washing operation; (c) a means attached to said compartment or compartments for the additive washing material of the unit dose container for opening said compartment or compartments for the washing additive and thereby releasing the contents of said compartment or compartments for the washing additive. to the aqueous wash solution in said drum; (d) a means attached to said receiver structure or to said rinse additive compartment or compartments of said unit dose container or both, to open said rinse additive compartment or compartments and in this way releasing the rinsing additive content thereof in said receiving structure; the means for opening said rinsing additive compartment is activated by means of the centrifugal force applied to said rinsing additive compartment or compartments during the spinning cycle that occurs during the operation of said automatic washing machine; and (e) means for transferring said rinse additive material from said receiver structure to the aqueous rinse solution formed in said washer drum during the rinse cycle of said fabric washing operation.

BRIEF DESCRIPTION OF THE FIGURES Figures 1 A and 1 B show top and bottom views of a type of two unit dose compartment insert that can be used in the present invention. Figures 2A and 2B show top and bottom views of another type of three unit dose unit insert that can be used in the present invention. Figure 3 shows a perspective view of a unit dose insert positioned within a rigid receiver structure suitable for the practice of the present invention.

Figures 4A to 4C show three side views of the insertion and the use of a unit dose multi-compartment insert in a modality of a rigid receiving structure with lid suitable for the practice of the present invention.

DETAILED DESCRIPTION OF THE INVENTION The invention provides a method for washing fabrics in an automatic washing machine. The automatic washing machine comprises a drum in which the fabrics are placed for washing. The aqueous wash solution and the aqueous rinse solution are formed in the drum. The washing operation in automatic washing machine has, as is conventional, at least one washing cycle. You can have more than one wash cycle. Frequently multiple wash cycles are described as a prewash cycle and a main wash cycle. In the following discussion, the aqueous wash solution is, in general, the solution in the main wash cycle, and in particular in the last wash cycle before the rinse cycle. Preferably, the laundry is contacted with the aqueous wash solution for about 1 to about 50 minutes, more preferably about 5 to about 40 minutes. Preferably, the operation also includes a spin cycle carried out after the wash cycle, during which the drum rotates, in general, at high speed. During the spin cycle the aqueous wash solution is removed from the drum of the washing machine. This is because in part to the gravitational flow of the wash water from the drum through an appropriate valve configuration. Certain elimination is also achieved by means of centrifugal force due to the rapid rotation of the drum. This centrifugal force displaces the water from the drum through holes or openings in the circumferential walls of the drum. These holes lead to drainage means that can be opened or closed. During the spin cycle, a large proportion of the aqueous wash solution in the drum is removed from the drum. Preferably, about 50 to about 99% of the aqueous wash solution is removed, more preferably from about 60 to about 90% of the aqueous wash solution. After the initial spin cycle, clean water is added back to the drum in a rinse cycle. In this invention, sufficient acid source is added to the rinse solution to bring the pH of the rinse solution to the range of from about 4 to about 7, preferably from about 4.5 to about 6.5. The operation of the washing machine may comprise more than one spin cycle and / or more than one rinse cycle. However, the invention requires that at least one of the rinse cycles be such that the rinse solution brings the pH to the required range. The pH of the rinse solution may be in the range of about 4 to about 7, preferably from about 4.5 to about 6.5, in all rinse cycles if more than one is used. In this case, although it is possible to add the source of acid to the solution of Rinse in each rinse cycle, it is also possible to add sufficient acid source in a rinse cycle so that the cycle and subsequent rinse cycles include rinse solution having the required pH. In methods that include more than one rinse cycle it is preferred that at least the final rinse cycle be such that the pH is in the range of about 4 to about 7, preferably about 4 to about 5.5. In particular, it is preferred that the acid source be added to the rinse solution in the final rinse cycle. As a less preferred alternative, the penultimate rinse cycle can be such that the rinse solution has a pH in the range of about 4 to about 7, preferably about 4.5 to about 6.5. It has been found that the benefits are greater if the acid source is added to the rinse solution after a significant proportion of the washing solution, containing the detersive surfactant component and the detergent additive component, has been removed from the washing machine. automatic The pH of the rinse solution is controlled in the desired range by the addition of an acid source. This can be selected from any acidic material or acid precursor compatible with the fabric being washed and with other components incorporated in the rinse cycle, if any, and the components of the detergent composition added to the wash solution. Inorganic acids can be used, but organic acids are preferred. Polymeric acids such as polyacrylic acid, polymaleic acid and copolymers of acrylic acid / maleic acid. However, the most preferred acids are mono or polypropic organic acids having an equivalent weight of not more than about 80. Particularly preferred are, for example, maleic acid, citric acid, and oxalic acid, with citric acid being especially preferred. . The acid level must be selected to achieve the pH value required in the rinse cycle. However, when low molecular weight organic acids are used, the concentrations in the rinse solution are, in general, in the range of about 100 to 1000 ppm. It has surprisingly been found that in the context of an automatic washing machine washing operation, the use of an acid pH in the rinse cycle, particularly a pH in the range of about 4.5 to about 6.5, leads to particular benefits. It has been discovered, for example, that the transfer of the dye to other fabrics is reduced. Therefore, the invention is suitable in particular for washing colored fabrics. Due to the reduction of the color transfer obtained by the invention, it can be applied in particular to the washing of a load of fabrics comprising at least some colored fabrics and at least some light fabrics. Another benefit is the reduction of waste accumulation in the fabrics. In dark fabrics this tends to manifest as a bleaching effect. The accumulation of waste can also affect white and other light fabrics, for example causing a "lackluster" appearance. The residue may be due mainly to the hardness of the water and essentially based on calcium. However, the waste may include combinations of these water hardness deposits with the body filth, detergent and / or softener and / or other washing actives and may be described in that case as complex filth. It has also been discovered that the low pH values in the method of the invention can themselves lead to improved soil removal. This can be applied in particular to bleach stains such as coffee, tea and wine. You can also see benefits in fatty spots and in spots that contain fat. You can also see benefits in spots susceptible to elimination by means of enzymes. These spots include those that contain protein susceptible to elimination by means of proteases, stains containing starch susceptible to elimination by means of amylases, and stains containing fat susceptible to elimination by means of lipases, in particular spots containing protein and containing starch. Examples of these are grass, blood and meat sauce. As a result, the method of this invention can be applied in particular to fabrics stained with any of these types of stains. In a particularly preferred embodiment of the invention, an additive material for rinsing is also added to the rinsing solution in addition to the acid source. It has surprisingly been found that the use of an acid pH rinse can provide particular benefits in terms of improving the properties of certain rinse additives.

Particular benefits arise when the rinse additive is a perfume or a perfume precursor (ie a material that decomposes or otherwise reacts in the rinse solution to produce a perfume molecule). It has been found that the inclusion of these materials as a rinse additive in a low pH rinse results in an improved deposit of the perfume in the fabric. Another preferred additive for rinsing is a chelating agent. In particular, the phosphonate chelating agents have good performance at acid pH. Thus, the inclusion of these chelating agents in an acid rinse cycle can improve the removal of stains and also improve the removal of the accumulated hard water deposits from the fabrics. In this way, these additives are especially preferred for use when the load includes colored fabrics, as discussed above in connection with the reduction of hard water deposits. Another preferred additive for rinsing is a fabric brightening agent. Especially preferred fabric brighteners are phthalocyanines, which exhibit a better deposit on the fabric at the pH required in the invention. Preferred brighteners include the acid-stable fluorescent rinsing agents such as Tinopal CBS manufactured by Ciba Geigy (disodium-4,4-bis- (2-sulphotryl) biphenyl). Another preferred group of rinsing additives is the group of beneficial fabric care agents, such as fabric softeners, touch modifiers and wrinkle modifiers. It has been discovered that these exhibit a better deposit on the fabrics and consequently, greater benefits for the fabrics, in the pH range used in this invention. Preferred softeners include quaternary esters, quaternary alkylammonium salts, clays, silicone oils, silicone polyols and aminosilicones. Other beneficial agents for fabric care include dye fixatives such as cationic oligomers, anti-abrasion agents such as silicone and cellulose and cellulose derivatives, and chlorine scavengers (which can reduce discoloration), such as amines, ammonium salts and reducing agents. Another preferred group of rinse additives is the group of soil release agents and soil repellent agents. These depend for their efficiency on the deposit on the fabric and the particular types exhibit a better deposition in the pH of the rinse cycle in the method of this invention. Polymeric dirt release agents, hereinafter "SRA" or "SRAs" may optionally be used in the present invention. If used, SRAs will generally comprise from about 0.01% to 10.0%, usually from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the composition. SRAs may include a variety of charged, eg, anionic or even cationic monomer units (see U.S. Patent No. 4,956,447), as well as uncharged monomer units, and the structures may be linear, branched or they can still have a form of star. SRAs may include finishing portions that are especially effective in controlling molecular weight or altering physical or surfactant properties. The structures and the distributions of the loads can be adjusted to apply to different types of fibers and textiles and for various detergent products or detergent additives. Suitable SRAs include a sulfonated product of a substantially linear ester oligomer of an oligomeric ester backbone of terephthaloyl and oxyalkylenoxy repeating units, for example as described in U.S. Pat. no. 4,968,451, dated November 6, 1990 from J.J. Scheibel and E.P. Gosselink. See U.S. Pat. no. 4,711, 730, of December 8, 1987 by Gosselink et al., For examples of those produced by means of the transesterification / oligomerization of methyl ether of polyethylene glycol, DMT, PG and polyethylene glycol ("PEG"). The fully anionic oligomeric esters and with US patent overlay. no. 4,721, 580 of January 26, 1988 from Gosselink, such as the oligomers of ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the oligomeric block non-ionic polyester compounds of US Pat. no. 4,702,857 of October 27, 1987 from Gosselink, for example produced from DMT, PEG with Me and EG and / or PG finishing, or a combination of DMT, EG and / or PG, PEG with Me and Na-dimethyl- 5-sulfoisophthalate; the anionic esters of terephthalate with cap, in particular sulfoaroyl, of the patent of The USA. no. 4,877,896, of October 31, 1989 by Maldonado, Gosselink et al. They can also be used as additives for rinsing. SRAs also include the copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene terephthalate, see U.S. Pat. no. 3,959,230 to Hays of May 25, 1976 and U.S. Pat. no. 3,893,929 of Basadur, July 8, 1975; cellulose derivatives such as Dow polymers; and the alkylcelluloses of d-C4 alkylcelluloses and hydroxyalkylcelluloses of C4; see U.S. Pat. no. 4,000,093 of December 28, 1976 by Nicol et al. Suitable SRAs characterized by hydrophobic poly (vinyl ester) ester segments include grafted copolymers of poly (vinyl ester), eg, C -? - C6 vinyl esters, preferably poly (vinyl acetate), grafted to main chains of polyalkylene oxide. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available examples include SOKALAN SRAs such as SOKALAN HP-22, available from BASF, Germany. Other SRAs are polyesters with repeating units containing 10-15% by weight of ethylene terephthalate together with 90-80% by weight of ethylene polyoxyterephthalate, derived from a polyoxyethylene glycol of average molecular weight 300-5000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI. See also U.S. Pat. no. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. Monomers Suitable for the aforementioned SRAs include sodium 2- (2-hydroxyethoxy) -ethanesulfonate, DMT, sodium dimethyl 5-sulfoisophthalate, EG and PG. Additional classes of SRAs include (I) non-ionic terephthalates which use isocyanate coupling agents to link the polymeric ester structures (see U.S. Patent No. 4,201, 824, Violland et al. US No. 4,240,918 Lagasse et al .;) (II) SRAs with carboxylate end groups made by adding trimellitic anhydride to known SRAs to convert the terminal hydroxyl groups to trimellitate esters. With an appropriate selection of the catalyst, the trimellitic anhydride forms bonds to the polymer terminals through a carboxylic acid ester isolated from the trimellitic anhydride instead of through the opening of an anhydride bond. The nonionic or anionic SRAs can be used as raw material as long as they have hydroxyl end groups that can be styrated. See U.S. Pat. no. 4,525,524 to Tung et al .; (III) SRAs based on terephthalate of the urethane-linked variety, see U.S. Pat. no. 4,201, 824, deViolland et al .; (IV) polyvinylcaprolactam and copolymers related to monomers such as vinyl pyrrolidone and / or dmethylaminoethyl methacrylate, including both nonionic and cationic polymers, see U.S. no. 4,579,681 to Ruppert et al .; (V) grafted copolymers, in addition to SOKALAN types of BASF made by grafting acrylic monomers on sulfonated polyesters; it is stated that these SRAs have dirt release and antiredepositing activity similar to those known cellulose ethers: see EP no. 279.134 A, 1988 by Rhone-Poulenc Chemie; (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate in proteins such as caseins, see EP 457,205 A of BASF (1991); (VII) the polyester-polyamide SRAs prepared by the condensation of adipic acid, caprolactam, and polyethylene glycol, in particular for the treatment of polyamide fabrics, see Bevan et al., DE 2,335,044 Unilever NV, 1974. Other useful SRAs are described in U.S. Pat. no. 4,240,918, 4,787,989, 4,525,524 and 4,877,896. All of the aforementioned patent references that refer to SRAs are incorporated herein by reference. The preferred dirt repellents are fluoropolymers and acrylate polymers. These types of additives have in particular high substantivity to fabrics under acidic conditions. It has been found that the benefits are obtained when the rinse additive is a bleach or a bleach catalyst or a mixture thereof. The preferred bleaches are the oxidative bleaches, ie those that generate hydrogen peroxide such as perborates and percarbonates. Like these sources of inorganic peroxygen, preferred bleach systems include organic peroxyacids. The sources of inorganic peroxygen can be combined with activators or bleach catalysts. Preferred bleach catalysts are those that do not require a formulated source of peroxide or oxygen.

However, it has been found that the use of the pH defined in the rinse step in the present invention allows lower levels of bleach and / or bleach activator and / or bleach catalyst to be used in the formulation applied to the wash cycle with obtaining equivalent results. For example, the level of percarbonate or perborate bleach (or other oxygen bleach) may be below 15%, preferably below about 12% and even about 10%, in combination with no more than about 3% of bleach activator such as TAED, in the formulations, such as powder detergents for use in horizontal drum washers, which would normally contain approximately 20% percarbonate or perborate and approximately 4% activating bleach. The level of percarbonate or perborate (or other oxygen bleach) bleach may be below 4%, preferably below 3% and even about 2.5%, in combination with not more than 5% bleach activator such as TAED , in the formulations, such as powdered detergents for use in vertical drum washers, which would normally contain about 5% percarbonate or perborate and about 6% activating bleach. In liquid detergent compositions the level of bleach such as PAP may be below 2%, compared to the more usual 3.5%. In some cases, this invention still allows the use of any source of bleach in the composition applied in the wash solution.

Another rinse additive is a color transfer inhibiting agent that prevents redeposition of color from one fabric to another. Preferred color transfer inhibiting agents are polyvinylpyrrolidone (PVP), poly-4-vinylpyrazine N-oxide (PVNO) and copolymers of N-vinyl-2-pyrrolidone and N-vinylimidazole (PVPVI). The aqueous wash solution contains a detersive surfactant component and a detergent additive component. In general, these are supplied to the aqueous wash solution as components of a laundry detergent composition. This can be in any appropriate form, for example in liquid form, powder, granules or tablet. A preferred physical form for the detergent composition is liquid. In particular, it is preferred that the pH obtained in the wash cycle be in the range of from about 7.5 to about 10, preferably from about 7.5 to about 9. In general, the detergent composition can contain any of the standard components of the compositions detergents As with detergent surfactants and detergent additives, the materials contained in the wash solution may include chelating agents, anti-redeposition agents, dispersants, suds suppressors, boosters, bleaches and enzymes. A more detailed description of suitable laundry additive materials can be found in publications WO 00/02982 and WO 00/02987, both incorporated herein by reference.

It has been discovered that the use of the acid rinse cycle in the method of the invention is especially beneficial when certain types of material are included in the detergent composition and therefore, are added to the aqueous wash solution in the wash cycle. For example, particular benefits arise when the detergent composition added to the wash cycle includes the PAP bleach and, preferably, a bleach catalyst. Other preferred bleaches are the C7 to C30 aromatic peroxy carboxylic acids and their precursors, preferably the C7 to C2o heteroaromatic peroxy carboxylic acids. Especially preferred examples include the phthalimidoperoxyhexanoic acid (PAP) mentioned above, described in the European patent application EP-A-349940, and other compounds of the formula: where n can have a value of 1 to 18. In PAP n is 5. The use of an acid rinse allows to minimize the level of bleach and activator in the wash and thus, the cleaning benefit that can be achieved with a certain dose of bleach / activator is maximized. Suitable bleach catalysts are described in publications WO 00/29537, WO 01/16271 and WO 02/68574, all incorporated herein by reference.

As discussed above, the use of an acid rinse is especially beneficial to maximize fat cleansing. In particular, the benefits are achieved when the detergent comprises anionic surfactants such as linear alkyl benzene sulphonates, nonionic surfactants such as alkyl ethoxylates or amine oxides, cationic surfactants such as quaternary alkylammonium surfactants and amphoteric surfactants such as betaines. The benefits of using an acid rinse include improved performance at low temperature. Thus, the preferred method is such that the maximum temperature of the aqueous wash solution and the aqueous rinse solution is not greater than about 60 ° C, preferably not more than 50 ° C, more preferably not greater than 45 ° C. In particular, the invention provides benefits wherein the wash solution is quite cold and in which the maximum temperature of the wash solution is not greater than about 35 ° C, preferably not more than 32 ° C. The invention also provides particular benefits when the washing solution and / or the rinsing solution are of relatively high degrees of hardness, since this washing and rinsing solution leads to particular waste deposit problems and results in discoloration of the fabrics of colors and the "dulling" of light fabrics and the formation of complex soils. Thus, the invention is especially beneficial when the hardness of the washing solution and / or rinsing solution is at least about 100 ppm of CaCO3.

It is particularly preferred that the method of the invention be carried out using suitable apparatuses for delivering the detergent compositions to the wash cycle and the additive rinse compositions to the rinse cycle. These preferred apparatuses are described in detail in the publications of PCT patent applications WO 03/69042 and WO 03/69043, both published on August 21, 2003. The descriptions of these PCT applications are incorporated herein by reference. Thus, in a preferred aspect of the invention, the method comprises: (a) Providing a unit dose package containing an additive rinse material for laundry washing; (b) inserting said unit dose package containing additive into a rigid receiving structure; (c) at the beginning of the operation of the automatic washing machine placing said receiving structure with said unit dose package containing additive therein, in the drum of said automatic washing machine in a location that puts it in significant contact with the aqueous solution of rinse during the rinse cycle; (d) operating the automatic washing machine through a process comprising a spin cycle between the at least one wash cycle and the rinse cycle to apply centrifugal force to said pack unit dose containing additive in said recipient structure; said centrifugal force serves to activate the opening means of the container attached to said container or said receiving structure or both, and in this way open said container, release the contents thereof, and hold said contents inside said rigid receiving structure; and after that (e) withdrawing the centrifugal force from said open container by ending the spin cycle during the operation of said automatic washing machine; and thereafter allowing the laundry additive material within said rigid receiving structure to pass by gravitational flow through the holes in said receiving structure to the aqueous rinse solution during the rinse cycle in the operation of said automatic washing machine. Another preferred aspect is a method comprising: (a) Placing a rigid receiving structure in the washing machine in a fixed spatial relationship to said washing machine drum whose receiving structure comprises a base and a lid that can be opened and closed for said base; (b) placing in said receiving structure with its lid open at the beginning of the washing operation, a multi compartment insert containing at least two different compartments thereof at least two different additive materials for washing clothes, of which one is added to the contents of the drum of the washing machine during the at least one washing cycle and one is added to the contents of the drum of the washing machine during the rinsing cycle; (c) closing the lid of said receiver structure with said insert within to thereby activate the medium attached to said rigid receiver structure to open at least a first compartment of the multi-compartment insert and thereby allow dispensing of the material in said compartment open to said drum of the washing machine; Y (d) operating said automatic washing machine through its operational cycle, including a spin cycle between the at least one washing cycle and the rinse cycle to thereby activate the medium attached to said receiving structure and / or With said multi-compartment insert for opening one or more additional compartments of said insert containing a laundry additive material different from said first previously opened compartment, said opening of said additional compartments occurs after the start of the spin cycle of said operation of the automatic washing machine, and said means for opening said additional compartments are activated by the centrifugal force that emerges from the centrifugation cycle; said opening also allows to dispatch the material in said compartment or open compartments to said drum of the washing machine. In particular, this last aspect is preferred. The rigid receiver structure used in this aspect of this invention must be positioned in a fixed spatial relationship to the drum of the washing machine. It is preferred to position the rigid receiver structure within the drum of the washing machine at a location such that it is in contact with the washing or rinsing water or that is added to the drum during the washing and rinsing cycles of the washing operation. The receiving structure can be positioned on or near the washing machine agitator (if any), on the floor (top loading washing machines) or on the rear wall (front loading washing machines) of the drum. Most preferably, however, the rigid receiving structure will be fixed to the inner circumferential wall of the washing machine drum in such a position as to allow it to come into contact with the water used in the cycle at least some time during the washing cycles. . In the case of American washing machines this position will preferably be below the water filling line in the drum. The rigid receiving structure will comprise a base member and a lid that can be opened and closed for said base. In general, this configuration will include an articulated lid on a three-dimensional base element. The three-dimensional base element can be dimensioned and configured to adequately hold the container of unit doses of multiple compartments containing the additive materials to wash clothes to be supplied. The rigid receiving structure must have a means attached thereto to open at least one of the compartments of the multi-compartment insert that fits therein. Such means are usually activated by closing the lid of the receiving structure once the multi-compartment unit dose insert has been placed within the structure. Said aperture means may comprise, for example, selectively located rupture or perforation means such as intense projections or blades piercing one or more of the compartments of the selectively positioned unit dose insert. The rupture or perforation means are then configured so that they move when the lid is closed so that this displacement produces the opening of the compartments of the insert that it is desired to open. Said opening means can be attached to the base of the receiving structure to the structure lid or to both. As an alternative, the opening means for the first compartment or compartments of the insert could comprise an arrangement of holes or openings in the receiving structure that open as the lid of the receiving structure is closed. The opening of the orifices or openings of the receiving structure could allow the water from the washing step to enter and dissolve those from inert compartments soluble in water or at least open by having water-soluble sealing means.

Preferably, the rigid receiver structure will also comprise a second means for opening additional compartments of the insert placed therein. Said additional compartments will comprise additive materials for washing clothes other than those of the first compartment initially opened as a consequence of closing the cover of the receiving structure. These second means for opening additional compartments of the unit dose insert are reactivated by means of the centrifugal force applied to the receiver structure during the spin cycle and as a consequence thereof when the washing machine is in use. Thus, for example, the second means for opening the additional compartments may also comprise intense projections, blades or blades that will strike additional compartments of the unit dose insert that must be opened during the spin cycle. Initially, the insert can be prevented from coming into contact with the second medium (up to the spin cycle), for example by placing a hinged or removable baffle plate or sheet within the receiver structure. Said baffle plate or sheet will hold the insert in a position such that its additional compartments do not hit the opening means of the second compartments upon initially closing the receiving structure. However, by applying a centrifugal force through the centrifuge cycle, it is possible to hold the insert by positioning the deflecting plate or plate in a position in which the second compartments will be displaced by the centrifugal force applied to a position such that the Opening means of the second compartment pierce the insert. As Alternatively, the second opening means for the additional compartments as well as the initial opening means, may comprise an element of the displaceable receiving structure that will open holes upon applying the centrifugal force of the spin cycle. The water that enters through these open orifices can then dissolve or in any other way open the additional compartments of the insert properly constructed and positioned. As with the opening means of the first compartment of the insert, the second means for opening additional compartments of the insert can be attached to the base of the receiver structure, the cover or both. The rigid receiver structure is also configured to allow water to eventually enter the structure during the various cycles of the laundry operation and to allow the contents of the open compartments of the insert to be supplied from the structure to the drum of the washing machine. In general, this configuration will include holes or openings in the receiving structure that allow the entry and exit of water from the washing operation through them and the passage of the additive materials to wash clothes in the drum of the washing machine. In a preferred configuration, the rigid receiver structure will be capable of holding substantially all of the content (at least about 90% by weight) of the rinse aid of the open insert of the spin cycle until the spin cycle is complete. In this way, the centrifugal force that opens the additional compartments of the insert, can also be used to sustain the contents that come from the open compartments within the structure and in some cases even within the open compartments of the insert until the spin cycle is complete. At the end of the centrifugation cycle and the centrifugal force ceases, gravity allows the contents of the open inserts to flow from the structure through holes in the "bottom" of the same. As an alternative, once the centrifugal force of the spin cycle has ceased and no more rinsing water is added to the drum, the released rinsing additive materials can be rinsed from the structure to the drum of the washer by rinsing water which then enters into the drum. the receiving structure. By having the structure hold the rinsing additives released until the spin cycle is complete, the additive material is prevented from being rinsed off! Washer drum forcing it out of the drum through drainage holes in the drum wall during the spin cycle. The opening of each of the several compartments of the insert in the receiving structure must allow the majority (at least about 85% by weight), and preferably all, the content of the open compartment in this way to be combined eventually with the water of washing or rinsing present in the drum of the washing machine during the cycle in which the compartment is opened. The wash water in the drum during the wash cycle will normally have supplied thereto from about 15 to 100 grams, preferably about 40 to 80 grams, of the laundry additive materials as a result of the opening of the compartment or compartments of the laundry. additive for insert wash. The rinsing water in the drum for any rinse cycle during which a rinsing additive compartment is opened in the insert will normally eventually have added thereto from about 5 to 50 grams, preferably from about 15 to 35 grams, of material rinsing additive as a result of the opening of the rinsing additive compartment or compartments. The rigid receiver structure can be built with any solid material including plastic, metal, ceramic, wood, etc., as long as it maintains its configuration and mode of operation during the wash cycle and stays in contact with the wash and wash water. used rinsing and with the additive washing materials released from the compartments of the unit dose insert. It is preferred to construct the rigid receiving structure with thermoformed plastic or injection molded plastic so that it is cost effective and can be produced in large quantities. The unit dose insert of multiple compartments should have a size and configuration such that it can function together with the rigid receiving structure to which it is attached and within which it is used. The unit dose insert will thus comprise at least two separate compartments, one for the laundry additive materials to be supplied in the wash water at the beginning of the washing operation and one for the rinse additive materials to be supplied in the washing operation. the following rinse cycles during the course of the washing operation. It is obvious that the unit dose insert can use more than one compartment for the additive materials of the washing water and more than one compartment for the additive materials of the rinse water. This can be useful when two wash or rinse water additive materials are incompatible with each other and it is desired to pack them separately until they are added to the drum of the washing machine. Each compartment of the unit dose insert can be constructed of water insoluble materials, water soluble materials or a combination of both. In addition some insert compartments can be constructed of insoluble materials in water while others can be constructed of water soluble materials. Additionally, the insert compartments can be flexible or rigid or have some flexible and other rigid compartments. If it is desired that the unit dose insert be rigid, it can be constructed of any conventional thermoformed or injection molded polymeric material. Thus, materials such as polyethylene, polypropylene, polystyrene or polyester (for example polyethylene terephthalate) could be used to form the multi-compartment insert. A polymeric material with a good thermal stability should be selected, especially if the insert is intended to be used in washing machines of European configuration where water with temperatures similar to those of boiling water is used. The insert material should also be inert to any chemicals present in the laundry additives that the insert supplies.

A preferred configuration for the unit dose insert comprises a rigid multi-compartment thermoformed tube formed of water insoluble plastic, such as for example polypropylene or polyethylene. The compartments of the rigid tube can be sealed with a thin layer of a perforable or breakable plastic or metal, eg a thin aluminum foil. In another preferred configuration, the bag containing the wash water additives can be flexible and made of water soluble materials, for example polyvinyl alcohol, and can at the same time be attached to a receptacle or compartment made of water-insoluble materials that contain the rinsing additive materials to be supplied later in the wash cycle. In a particularly preferred embodiment in the present, the multi-compartment insert itself may contain the opening means for the compartment or compartments containing the rinsing additive materials. These are the compartments that will be opened by means of the centrifugal force applied to the insert during the spinning cycle of the washing operation. Said rinse additive compartments may contain a frangible seal which is opened by increasing the pressure on the contents of the compartment as a consequence of the centrifugal force that is applied during the rotation. Alternatively, the means for opening the rinsing additive compartments may be part of a receiving structure as described above. It is obvious that the means for opening the rinsing additive compartments should be attached to the rigid receiving structure or the multi-compartment insert so that in one way or another the rinsing additive compartments are opened at the right time during the washing operation. The multi-compartment unit dose insert, the rigid receiving structure with lid and the relationship between them for use in the systems, methods and kits of the present are illustrated in greater detail in the accompanying figures. Figures 1A and 1B of the figures show top and bottom views, respectively, of a two compartment unit dose insert 11 that can be used in the practice of the present invention. This compartmentalized unit dose insert 11 can be made of insoluble rigid thermoformed polypropylene. It also has a main compartment 12 suitable for storing liquid laundry additive 17 such as liquid detergent often used to be supplied to the washing cycle of the laundry operation. The unit dose insert of the second compartment 11 also has a smaller compartment 13 suitable for holding laundry liquid additive 18, as a garment conditioning agent or pH control agents, for supplying the rinse cycle of the washing operation of the laundry. clothes. Before use, both compartments are sealed at the top with a perforable or breakable layer 14 of film or sheet covering both compartments 12 and 13. The construction material of the insert 11 is not rigid enough to prevent the two compartments rotate with each other around an axis 15 represented by the strip of material between both compartments. This rotation characteristic around an arc 16 makes possible the movement initiated by the centrifugal force and the subsequent perforation of the rinsing additive compartment 13 when the insert is placed inside a receiving structure as shown here in Figure 3. Figures 2A and 2B show respectively the top and base views of a three-compartment unit dose insert 20 that can be employed in the practice of the present invention. This three-compartment unit dose insert 20 includes a large compartment 21 that holds a laundry detergent liquid 27 and a smaller compartment 22 that holds a granular product of peroxide compound bleaching agent 28. The contents of the compartments 21 and 22 are incompatible with each other if combined before use; said contents are supplied approximately simultaneously to the washing cycle by opening both compartments at the beginning of the washing operation. The third compartment 23 holds a liquid additive product for rinsing 29. This rinsing additive product 29 is the last to be supplied in the rinse cycle of the laundry operation, and includes a pH adjusting agent to carry the Rinse at the required acidic pH. As in the two-compartment unit dose insert of Figures 1A and 1B, the compartments of Figures 2A and 2B of the unit dose insert 20 are sealed at the top with a perforable or breakable film or sheet (not shown). sample) before inserting the unit dose 20 into a receiving structure for use in accordance with this invention. In addition, as with the insert of Figures 1A and 1B, the unit dose inserts of Figures 2A and 2B 20 have an axis 25 between the wash additive compartments 21 and 22 and the rinsing additive compartment 23 around from which the rinsing additive compartment 23 can rotate relative to the compartments 21 and 22 following an arc 26. This rotating characteristic around the arc 26 allows the eventual movement induced by the centrifugal force and consequently, the eventual perforation of the acid compartment of rinsing additive 23 when the insert 20 is positioned in a receiver structure as illustrated below in Figure 3 and Figure 4A, and Figures 4B and 4C. Figure 3 shows a perspective view of an insert 30, as shown in Figures 1A, 1B, 2A and 2B, which has been inserted into a receiving structure with cover 31 that has been closed with insert 30 within it . The receiving structure 31 comprises a base plate 32 surrounded by a side wall structure 33 fixed to the base plate 32. A cover 34 completes the receiving structure and is fixed to the side wall structure 33 by means of a hinge 35. Further details of the internal components of the receiving structure 31 are shown in the transparent side views of Figures 4A, 4B and 4C. Figures 4A, 4B and 4C show transparent side views of an insert 40, as shown in Figures 1A, 1B, 2A and 2B, inserted into a receiver structure 41. In Figures 4A to 4C, the receiving structure is shown. 41 comprising a base which comprises a base plate 42 and a side wall structure 43 fixed to the base plate 42. A cover 44 for the receiver structure 41 is attached to the side wall structure 43 on the hinge 45. The base plate 42 comprises means for fastener 60 which are used to fix the receiving structure 41 to the inner wall of the drum of an automatic washing machine (not illustrated). The receiving structure 41 is fixed to the drum of the washing machine so that the base plate 42 remains parallel to the axis of the drum of the washing machine and perpendicular to the direction of the centrifugal force arising during the spinning cycle of the washing machine. Figure 4A depicts the receiver structure 41 in an open position with the insert 40 partially inserted. Figure 4B shows the receiving structure 41 in a still open position but with the insert 40 inserted therein in its entirety. Figure 4C shows the receiving structure 41, with the insert 40 as illustrated above in Figure 3. In all three views of Figure 4A-4C, the insert is shown. 40 comprising compartments for washing additive 70 and rinsing additive compartments 71. Insert 40 is inserted into the receiving structure with rinsing additive compartments 71 positioned in the hinge direction of the receiving structure lid. As shown in Figures 4A to 4C, the receiving structure 41 also comprises an articulated plate 46. This articulated position plate 46 is fixed or guided within the wall structure 43 by means of a clamping means 47. This position plate 46 is supported also on a medium containing a compressible pivot point 48. The positioning plate 46 is articulated at the hinged point 49 near the middle of the compressible pivot point 48. The position plate 46 also includes tabs 50 at the end of the additive of washing opposite the clamping means 47. These tabs 50 fit into the guide grooves 51 in each of the walls opposite the side wall structure 43. By closing the lid 44 it activates the rotation of the articulated plate 46 position around from its point of articulation 49 and at the same time depresses the middle of the compressible pivot point 48. The end of the washing additive of the position articulated plate 46 thereby rotates towards the base plate 42 and is held in the closed position by means of a closing mechanism 52 attached to the base plate 42. In this way, when closing the lid 44 the rotation of the additive end of the articulated position plate 46 is guided by the tabs 50. in the slots 51 as if it were an array of cams while the structure is placed in the locked position. As a consequence of the closing and locking, the compartments of the washing additive 70 of the insert 40 strike the sharp and cylindrical drilling means of the washing additive 53 attached to the base plate 42. This action perforates the compartments of washing additives 70 of the insert 40 releasing the contents of the washing additive thereof into the receiving structure 41. As shown in Figure 4C, this action also serves to position the rinsing additive compartments 71 of the insert 40 above, but not in contact with the cylindrical drilling medium of the rinsing additive 54, also attached to the base plate 42. Later in the washing operation, during the spinning cycle, the centrifugal force generated by the cycle The centrifuge means causes the rinsing additive compartments 71 of the insert 40 to rotate toward the base plate 42. This action subsequently causes the rinsing acid additive compartment 71 of the insert 40 to affect the additional piercing means of the rinsing additive compartment. 54 also attached to the base plate 42. In this way, the rinsing acid additive compartment 71 of the insert 40 is broken, releasing in its content in the receiving structure 41. The side wall receiving structure 43 contains holes 61 a through which the contents released from the compartments of the insert flow into the drum of the washing machine. In the same way, the lid 44 contains holes 62 for the same purpose. The rinsing additive released by the centrifugal force is held at the base of the receiver structure 41 until it stops. The released rinsing additive can then flow by gravity through the holes 63 in the hinged end of the cover of the receiving structure 41 and in the drum of the washing machine.

EXAMPLE I The following table shows the Composition A, a composition especially suitable to be added to an automatic washing machine top of a single rinse cycle. Also shown is Composition B which is especially suitable for adding to the final rinse cycle in a front-loading automatic multi-rinse cycle washer. 30 grams of each composition are added to the relevant rinse cycle.

Neodol 23-5 (non-ionic surfactant) 3.3 3.3 Perfume 1.3 1.7 • jO Water balance balance EXAMPLE II A three-compartment unit dose insert having the general configuration shown in Figures 2A and 2B is prepared. The 5 insert is made of 0.381 mm thick polypropylene, developed through a thermoforming process. The insert formed in this manner is 11.0 cm in length, 7.0 cm in width and 2.5 cm in thickness and includes the three compartments, 21, 22 and 23 shown in Figures 2A and 2B. Approximately 55 grams of a high performance liquid or aqueous detergent (HDL) product is placed in the largest compartment of the wash additive 21 of the insert of Figures 2A and 2B. Said HDL comprises approximately 40% by weight of anionic and nonionic surfactants, 8% by weight of organic additives, 19% by weight of solvents organic and other ingredients such as borax and enzymes in smaller quantities. Approximately 11 grams of a liquid bleaching composition are placed in the smallest compartment of the wash additive 22 of the insert of Figures 2A and 2B. This composition comprises 17% by weight of an aqueous slurry of d-phthalimidoperoxyhexanoic acid (PAP) together with minor amounts of perfume. Approximately 30 grams of an acid rinse additive are placed in the rinse additive compartment 23 of the insert of Figures 2A and 2B. This aqueous liquid additive composition for rinsing comprises about 22.4% by weight of maleic acid and minor amounts of nonionic surfactant and perfume, as shown above in Composition A in Example I. The insert with the compositions in each of The three compartments, as described above, are sealed with a 0.0304 mm layer of oriented polypropylene film placed over the open compartments. The sealed package of the unit dose insert is subsequently placed in a rigid receiving structure with lid of the type shown in Figures 3 and 4A to 4C. Prior to inserting the unit dose insert package, this rigid receiver structure is attached to the circumferential wall of the vertical drum of a Kenmore 70 Series automatic top loading washer. The receiver structure joins approximately 20 cm from the floor of the drum with the lid hinge more near the floor of the drum and with the back plate of the structure parallel to the circumferential wall of the drum. In this way, the open end of the receiving structure is oriented towards the top of the washing machine. With the receiving structure with lid in open configuration, the three-unit unit dose insert is placed therein as illustrated in Figures 4A and 4B. Then the clothes to be washed are placed in the washing machine. Just before starting the washing machine in its washing cycle, the cover of the receiving structure is closed, providing the structure and insert configuration as shown in Figure 4C. Then the washing machine cycle starts. Closing the lid of the receiving structure with the insert within causes the perforating means of the washing additive 53 (Figures 4A to 4C) to break the layer of sealing material covering each of the additive compartments 21 and 22 (FIGS. 2A and 2B) of the insert. Said rupture releases the ingredients of the washing additive in the washing water that fills the rigid tube at the beginning of the washing cycle. The ingredients of the washing additive are cast from the receiving structure through the holes 61, 62 and 63 (Figures 4A to 4C) in the walls of the receiving structure, thereby providing washing water to which they have been added 66 grams of washing additive ingredients (HDL plus bleach). The washing solution formed in this way has a pH of about 8.5. After a wash cycle of approximately 14 minutes, the washing machine starts with its spin cycle to eliminate washing water of the drum. The centrifugal force generated by this spin cycle serves to push the sealed rinsing additive compartment 71 (Figures 4A to 4C) of the insert into the receiver structure against the rupture means of rinsing additive 54 (Figures 4A to 4C) that form part of the rigid receiving structure. This action causes the rinsing additive compartment seal 71 (Figures 4A to 4C) to break and release the maleic acid-containing contents of the rinsing additive compartment to the receiving structure. This continued centrifugal force of the spin cycle sustains the acid rinse additive composition in an area of the receiving structure where there are no orifices so that the acid rinse additive remains in the receiver structure during the spin cycle. Two minutes after the centrifugation cycle has started, the drum of the washing machine stops rotating and begins to fill with rinse water. At the same time, the maleic acid additive composition for rinsing which has been held in the receiver structure during the spin cycle flows from the receiving structure mainly through the holes 63 (Figures 4A to 4C) and the water rinse. The rinsing water in and entering the drum can now also enter the receiving structure and wash any residual additives for acid rinsing from the open rinsing additive compartment. In this manner, approximately 30 grams of the acid rinse additive composition is introduced into the rinse water in the washing machine drum. This amount is sufficient to provide a rinse water pH of about 5.5 during the rinse cycle.

The rinse cycle continues for 5 minutes and after this, the garments inside the drum are dried by rotation in the final spin cycle. The wash and rinse additives of the insert have been sequentially supplied to the wash and rinse cycles respectively during the washing operation. This sequence addition! of these types of ingredients provides a pH profile for the washing operation that ranges from a pH of 8.5 in the wash solution to a pH of 5.5 in the rinse water during the rinse cycle.

Claims (19)

NOVELTY OF THE INVENTION CLAIMS

1. A method for washing fabrics in an automatic washing machine having a drum, wherein the automatic washing machine is put into operation to cause it to work through at least one wash cycle and at least one rinse cycle; the method comprises: (a) during the at least one wash cycle forming an aqueous wash solution containing a detersive surfactant component and a detergent additive component in the drum; the aqueous wash solution has a pH greater than about 7; (b) contacting the fabrics to be washed with the aqueous wash solution in the drum; (c) during the rinse cycle, form an aqueous rinse solution in the drum and contact the fabrics with the rinse solution; and (d) adding to the rinse solution sufficient acid source to bring the pH of the rinse solution to the range of about 4 to about 7.

2. The method according to claim 1, further characterized in that it comprises contacting the laundry to wash with the aqueous wash solution for about 1 to about 50 minutes, remove approximately 50% to 99% of the aqueous wash solution from the drum during a spin cycle performed between the cycle of washing and the rinse cycle, and contact the fabrics with the aqueous rinse solution for approximately 1 to 20 minutes.

3. The method according to claim 1, further characterized in that it also comprises adding to the rinse solution an additive material for rinsing laundry.

4. The method according to claim 3, further characterized in that the rinse additive is a perfume or perfume precursor.

5. The method according to claim 3, further characterized in that the rinse additive is a chelating agent.

6. The method according to claim 3, further characterized in that the rinsing additive is a fabric brightening agent.

The method according to claim 3, further characterized in that the rinse additive is a beneficial agent for the care of fabrics selected from softness, touch and wrinkle modifiers.

The method according to claim 3, further characterized in that the rinsing additive is a soil release agent or soil repellent agent.

The method according to claim 3, further characterized in that the rinse additive is a bleach or bleach catalyst.

10. The method according to claim 1, further characterized in that the washed fabrics comprise stained fabric with spots selected from bleaching spots, grease stains and spots susceptible to be removed with enzymes.

11. The method according to claim 1, further characterized in that the washed fabrics comprise colored fabrics.

The method according to claim 1, further characterized in that the maximum temperature of the aqueous wash solution and the aqueous rinse solution is not greater than about 60 ° C.

The method according to claim 1, further characterized in that the hardness of the water used to form the aqueous wash solution and the aqueous rinse solution is at least about 100 ppm as CaC 3.

The method according to claim 1, further characterized in that the aqueous wash solution is supplied by adding a detergent composition to the water in the form of a liquid and wherein the pH of the aqueous wash solution supplied in this way is not greater than about 10.

The method according to claim 1, further characterized in that the aqueous wash solution is formed by adding to the water a detergent composition comprising a surfactant selected from anionic, nonionic, cationic and amphoteric surfactants, of selected preference of linear alkylbenzene sulfonates, alkyl ethoxylates, amine oxides, quaternary alkylammonium salts and betaines.

16. The method according to claim 1, further characterized in that the method further comprises: (a) providing a unit dose package containing an additive rinse aid for laundry; (b) inserting the unit dose package containing additive into a rigid receiving structure; (c) at the beginning of the operation of the automatic washing machine, position the receiving structure, with the unit dose container containing additive therein, inside the drum of the automatic washing machine at a location that puts it in significant contact with the aqueous solution rinse during the rinse cycle; (d) operating the automatic washing machine through a process comprising a spin cycle between the at least one wash cycle and the rinse cycle to thereby apply centrifugal force to the unit dose pack containing additive in the receiving structure; the centrifugal force serves to activate the opening means of the container attached to the container or to the receiving structure or both, and thereby open the container, release the contents thereof, and hold the contents in the rigid receiving structure; and thereafter (e) removing the centrifugal force from the open container terminating the spin cycle during the operation of the automatic washing machine; and after that (f) allowing the additive material to wash clothes in the rigid receiving structure pass through gravitational flow through the openings in the receiving structure to the aqueous rinse solution during the rinse cycle in the automatic washing machine operation.

The method according to claim 3, further characterized in that the method further comprises: (a) positioning a rigid receiving structure in the washing machine in a fixed spatial relationship to the washing machine drum whose receiving structure comprises a base and a lid that can open and close for the base; (b) placing in the receiving structure with its lid open at the beginning of the washing operation, a multi-compartment insert containing in at least two different compartments thereof at least two different additive materials for washing clothes, of which one is added to the contents of the drum of the washing machine during the at least one washing cycle and one is added to the contents of the drum of the washing machine during the rinsing cycle; (c) closing the lid of the receiving structure with the insert within thereby to activate the medium attached to the rigid receiving structure to open at least a first compartment of the multi-compartment insert and thereby allow the delivery of the material in the compartment open to the drum of the washing machine; and (d) operating the automatic washing machine through its operational cycle, including a spin cycle between the at least one washing cycle and the rinse cycle to thereby activate the medium attached to the receiving structure and / or to the insert of multiple compartments to open one or more additional compartments of the insert containing additive laundry material, different from the first previously opened compartment; the opening of the additional compartments occurs after the start of the spin cycle of the operation of the washing machine, and the means for opening the additional compartments is activated by means of the centrifugal force arising from the spin cycle; the opening also allows to supply the material in the compartment or open compartments to the drum of the washing machine.

18. A system for providing the sequential addition of washing additives and rinse additives to the washing and rinsing cycles, respectively, of a fabric washing operation performed in an automatic washing machine containing a drum; the system comprises: (a) a unit dose package comprising at least one compartment containing washing additive material comprising a detersive surfactant component and a detergent additive component, the washing additive material serving to provide an aqueous wash solution having a pH greater than about 7; and at least one additional compartment containing a source of acid sufficient to bring the pH of the rinse solution formed during the rinse cycle to a pH of from about 4 to about 7; (b) a rigid receiving structure in which at least the rinsing additive compartment or compartments of the unit dose can be inserted at the beginning of the washing operation, the receiving structure is placed inside the drum of the automatic washing machine in a location that puts it in significant contact with the wash and rinse water during the washing operation; (c) a medium attached to compartment or compartments of washing additive material of the unit dose container for opening the washing additive compartment or compartments and thereby releasing the contents of the washing additive compartment or compartments in the aqueous washing solution in the drum; (d) a medium attached to the recipient structure or to the rinse additive compartment or compartments of the unit dose container or both to open the rinse additive compartment or compartments and thereby release the rinse additive therein into the structure The centrifugal force applied to the rinsing additive compartment or compartments during the spin cycle that occurs during the operation of the automatic washing machine activates the opening means of the rinsing additive compartment.; and (e) means for transferring the rinsing additive material from the receiving structure to the aqueous rinsing solution formed in the drum of the washing machine during the rinsing cycle of the fabric washing operation.

19. The system according to claim 18, further characterized in that the source of acid is sufficient to bring the pH of the rinse solution to the range of about 4.5. to 6.5.