ES2295789T3 - COADYUGANTES COMPOSITIONS OF THE CLEARING. - Google Patents

Abstract

A substantially non-aqueous concentrated rinse-aid composition for the heat-free drying of plastic-ware and other dishwashing items, the composition comprising at least 20% by weight of one or more super-wetting surfactants. The composition provides excellent finishing and care of the dishwashing load.

Description

Compositions of rinse aid.

Technical field

The present invention relates to the field of dishwashing, in particular refers to compositions rinse aids and uses thereof. The compositions provide advantages of drying, finishing and care for washed items.

Background of the invention

Currently the consumer not only expects a good cleaning by the dishwashing process but also a good finish of the cleaned items. The process it should also be soft enough to prevent damage to the articles. The variety of materials cleaned in the Dishwasher is gradually increasing. Traditional charges They mainly included glass, ceramic and metal items. The Current charges increasingly include more plastic items as well as Some wooden items.

An unmet need in the process of Dishwashing is the finishing of plastic items, especially drying. Usually at the end of the process of dishwasher washing plastic items are still wet and require another stage of manual drying or drained before to be saved

Other problems that currently exist in the dishwashing process refer to care and appearance of cleaned items. The washing process in dishwasher can favor corrosion of glass and metal and damage items with drawing and wood. An additional problem is refers to the appearance of the items cleaned since sometimes they have an absence of shine and a matt appearance, especially Glass and metal items. Another common problem is the white spots on teflon items.

US4005024, WO96-08553 and EP875556 refer to compositions rinse aids and patents US6362149, DE10136002 and EP687720 refer to dishwashing compositions.

US Patent 5,603,776 provides a method to clean plastic objects in a dishwasher comprising contacting the objects of plastic with an aqueous rinse solution comprising from 2 to 100 ppm of a non-ionic surfactant, 0.01 to 10 ppm of a surfactant of the fluorinated hydrocarbon type and from 0.01 to 10 ppm of a polydimethylsiloxane modified with poly (alkylene oxide). Without However, the method of this patent does not solve the problems described above herein.

In view of these problems, there is the need for a dishwashing method that provides a good  Finishing of cleaned items and at the same time avoid or Reduce damage to items.

Summary of the invention

According to the present invention, a multiphase unit dose product as defined in the claim 1. The composition comprises at least 20%, more preferably at least 25%, by weight of one or more surfactants super moisturizers, as defined herein more ahead.

The expression "practically non-aqueous" in This report includes compositions that contain less than 20%, preferably less than 15% and more preferably less than 10% water by weight of the composition.

The compositions of the present invention are apply in the aqueous rinse cycle of a dishwasher and are capable of completely drying plastic objects and other items for dishwashers during the subsequent drying cycle without applying hot. More especially, it is said that a composition is useful for "heat-free drying of plastic objects and other items for dishwashers "when a rinse concentration of less about 450 ppm, for example less than about 350 ppm, preferably less than about 300 ppm and more preferably less than about 200 ppm, it provides a Total drying of a polypropylene plastic sheet or 20 cm by 15 cm polystyrene after being placed vertically in the top of a GE500 dishwasher with the program "normal" at a temperature of 37-50 ° C without heating during the drying cycle.

The plastic sheet is visually evaluated 5 minutes after the end of the program (during this time the dishwasher is kept closed). Total drying is achieved When the plastic sheet has less than 5 droplets, preferably less than 3 droplets and more preferably none droplet at all. Plastic is one of the most surfaces difficult to dry between existing surfaces in a load typical of a dishwasher and therefore it is expected that if the plastic dries under certain conditions (including the presence of rinse aid), other items will too.

A surfactant is generally considered to be "superhumidifying" if a drop of an aqueous solution of 0.3%, preferably 0.03%, by weight of the surfactant extends spontaneously forming a virtually uniform film on a flat and smooth plastic surface (e.g. polypropylene or polystyrene) in less than about 10 minutes, preferably in less than about 5 minutes, more preferably in less than 3 minutes and especially in less than 1 minute. For the purposes of this invention it can be assessed whether a surfactant is super-moisturizing or not by the following method: With a micropipette a drop is created, preferably a 20 µl drop of the aqueous solution (water distilled) of the surfactant to be analyzed and deposited is on a flat and flat horizontal surface of polypropylene or polystyrene (for example a quality Petri dish) "polystyrene glass marketed by SPI) prewash with distilled and dried water at room temperature, that is, at 20 ° C with 30% -40% humidity. The distance between the drop that falls justly of the tip of the micropipette and the surface is approximately 3 mm After a specified time the diameter of the drop (or strictly the area of the surface moistened by the drop) with the help of an image capture medium (camera photographic) or with the naked eye (a grid is placed under the plate of Petri to measure the diameter of the drop). Then you Repeat the test using a drop of pure (deionized) water. Be considers that a surfactant is superhumidifying if the factor of dispersion (diameter of the surfactant solution / diameter of the pure water solution) is greater than about 2, preferably greater than about 3, more preferably greater than about 4 and especially greater than about 8, after 5 minutes, preferably after 3 minutes and more preferably after 1 minute.

Preferably the surfactants super-humectants (0.3% aqueous solution, preferably 0.03%) have a contact angle of less than approximately 15 °, preferably less than approximately 13 ° and more preferably less than about 11 °, on a polypropylene or polystyrene surface. Preferably the compositions of the invention (0.3% aqueous solution, preferably 0.03%) have a contact angle of less than approximately 16 °, preferably less than about 14º, on the surface of polypropylene or polystyrene.

The contact angle can be measured by preparing an aqueous solution comprising 0.3%, preferably 0.03%, in weight of the surfactant solution or adjuvant composition of the rinse to be measured. A measuring kit of contact angle FTA 200 from First Ten Angstroms. The measurements are performed at room temperature in a 2 cm x 5 cm piece of polypropylene (thin natural-colored plastic material marketed by Plastic Shims & Gaskets Co. LTD.) or in strips of polystyrene. With a syringe a drop of the solution on a strip of polypropylene or polystyrene. The distance between the strip and the tip of the syringe is approximately 3-5 mm. The images of the dispersion are taken with a high speed CCD camera and analyzed with the FTA 200 software.

Preferably, the compositions and the superhumidifying surfactants of the present invention meet the previous trials in at least one and preferably in both surfaces mentioned above, being polypropylene the preferred one.

Surfactants super-moisturizers suitable for use in the The present invention includes a series of surfactants of the type siloxane and hydrocarbon type. The superhumidifying surfactant is selects from the group consisting of: i) polyoxyalkylenesiloxanes wherein the poly (alkylene oxide) residue has the formula general (EO) n (PO) m, where EO is ethoxy, PO is propoxy, n is at least 3 and greater than m; ii) alcohols nonionic ethoxylates having an average of 4 to 10 moles of EO per mole of alcohol and an average chain length of 6 to 15 atoms carbon; iii) and mixtures thereof. Surfactants non-ionic alkyl ethoxylated super humectants are preferably free of propoxy groups.

Preferably the adjuvant compositions of the rinse of the present invention comprise a surfactant assistant. The auxiliary surfactant is not superhumidifying in itself. (neither on the polypropylene surface nor on the polystyrene surface according to the aforementioned tests) and is mainly used by Two reasons: i) as a synergist or extender to minimize the amount of super wetting surfactant needed to achieve a total drying; and / or ii) to suppress foam in the case of super-wetting surfactants foam formers The auxiliary surfactants suitable for the first reason include nonionic alkyl type surfactants ethoxylated / propoxylated having a degree of ethoxylation greater than degree of propoxylation and they have an average of 4 to approximately 9 moles of EO per mole of alcohol, 1 to 4 moles of PO per mole of alcohol and preferably at least 25%, more preferably at least 75%, of surfactant having a chain linear alkyl and containing 6 to 15 carbon atoms. These auxiliary surfactants preferably have a tension surface area of approximately 35 to approximately 27 mN / m measured in a 1% by weight aqueous solution at 20 ° C. Preferably these Auxiliary surfactants are low foaming.

The auxiliary surfactants suitable for the second reason (non-ionic soaps suppressants) include nonionic surfactants that have a cloud point low.

Preferably the auxiliary surfactants they have a contact angle (0.3% aqueous solution, preferably 0.03%) from about 17 ° to about 35 °, preferably from about 18 ° to about 22 °, on a polypropylene surface.

In a preferred embodiment the composition comprises at least 20% by weight of the composition of a surfactant of the superhumidifying siloxane type and an auxiliary surfactant, being the superhumidifying surfactant and the auxiliary surfactant in a ratio of about 1: 1 to about 1: 5, preferably about 1: 2. A preferred composition according to this embodiment it comprises from 20% to 40%, preferably from 20% to 30%, by weight of the composition of a surfactant siloxane type superhumidifier, especially methyltrisiloxane (and is preferably practically free of surfactant non-siloxane superhumidifier) and 30% to 70%, preferably from 40% to 60%, by weight of the composition of a auxiliary surfactant, preferably an auxiliary surfactant not ionic type ethoxylated / propoxylated alkyl.

In another preferred embodiment the composition comprises a suds suppressor as an auxiliary surfactant,  the superhumidifying surfactant and the auxiliary surfactant being in a ratio of about 5: 1 to about 1: 1.

Preferably the compositions of the invention also comprise one or more additional ingredients selected from the group consisting of: organic vehicles, antifoaming agents, humectants, dispersants, inhibitors of crystalline growth and mixtures thereof. The compositions comprising dispersants or growth inhibitors Crystalline are especially preferred because they reduce / prevent formation of watermarks on dried objects.

The compositions of the invention preferably they have a pH of about 6 to about 8 measured in a 1% by weight aqueous solution at 20 ° C. This is especially favorable for compositions comprising a Siloxane type surfactant because they are not stable at alkaline pH nor at acidic pH.

According to the invention, a product is provided of unit dose comprising at least two phases where one of The phases comprise the rinse aid composition of the invention and a means to release the composition to the cycle of rinsing of a domestic dishwasher. Preferably at least one of the phases that does not comprise the adjuvant composition of the rinsed, comprises a detergent for the main wash of the dishwasher, preferably containing a dispersant or crystal growth inhibitor.

Detailed description of the invention

The present invention provides compositions rinse aids capable of providing excellent level of finishing and care to load the dishwasher. The compositions provide a total drying of the objects of plastic, even without heat application during the cycle of drying, and also prevent the formation of spots on the Teflon surfaces, corrosion of metals or damage to drawings and take care of glass and wood objects.

The rinse aid compositions of the invention comprise superhumidifying surfactants and optionally auxiliary surfactants, organic vehicles, suds suppressors, humectants, dispersants, crystal growth inhibitors, adjuvant ingredients of conventional rinsing and mixtures thereof.

1. Superhumidifying surfactants

Surfactants super-humectants for use in the present invention are selected from the group consisting of i) modified siloxane with poly (alkylene oxide), preferably methylsiloxane, surfactants containing 1 to 9, preferably 3 to 6 and more preferably 3, siloxane moieties wherein the poly (oxide residue)  alkylene) has the general formula (EO) n (PO) m where n is at least 3 and greater than m; ii) ethoxylated alcohol type non-ionic surfactants which have an average of 4 to 9 moles of EO per mole of alcohol and a average chain length of 6 to 15 carbon atoms; iii) and mixtures thereof. The surfactants belonging to the Groups i) and ii) are described herein below. (subsections 1.1 and 1.2, respectively).

1.1 Surfactants of the polyoxyalkylene siloxane type

The polyoxyalkylene siloxanes suitable for use in the present invention have a residue of poly (oxide of alkylene) of formula (EO) n (PO) m in where n is at least 3 and greater than m, where EO is ethoxy, PO propoxy and n and m are averages. Preferably, n is about 3 to about 9, more preferably about 4 to about 8, and m is about 0 to about 4, preferably 1. Trisiloxanes are very preferred.

The preferred trisiloxane type surfactant of use in the present invention is a modified dimethyltrisiloxane with poly (alkylene oxide), preferably a methyltrisiloxane linear in which polyethers have been grafted by a reaction of hydrosilation. This process produces a copolymer with alkyl pendant (AP type), where poly (alkylene oxide) groups they are attached along the main siloxane chain through of a series of hydrolytically stable Si-C bonds. The siloxane type surfactants described herein are marketed under the Silwet® brand by Union Carbide or with the ABIL® polyethersiloxanes brand by Goldschmidt Chemical Corp. Los Preferred siloxanes for use in the present invention are Silwet L77, Silwet L7280, Silwet L7607 and Silwet L7608. Silwet L7280 is Especially preferred for its environmental profile. Others Suitable siloxane surfactants are those marketed by Degusa (with references 5840, 5847 and 5878), Dow Corning (with references DC 5211 and DC5212) and Waker (with reference LO66).

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These compounds are also known by the name of polyoxyalkylene-siloxane copolymers, siloxane polyethers, copolymers of poly (oxide of alkylene) -silicone, copolymers of silicone-poly (oxyalkylene), copolymers (or surfactants) silicone glycol.

Type surfactants Preferred polyoxyalkylenemethylsiloxane for use herein invention have a surface tension of less than 25 mN / m, preferably less than 22 mN / m, measured in an aqueous solution 1% by weight at 20 ° C.

1.2 Non-ionic surfactants of the alcohol type ethoxylated

Alkylethoxylated condensation products of aliphatic alcohols with an average of about 4 to about 10, preferably about 5 to approximately 8 moles of ethylene oxide per mole of alcohol are suitable for use in the present invention. The alkyl chain of aliphatic alcohols generally contains about 6 to about 15, preferably of about 8 to about 14, carbon atoms. Especially preferred are the condensation products of alcohols having an alkyl group containing about 8 to about 13 carbon atoms with a average of about 6 to about 8 moles of oxide ethylene per mole of alcohol. Preferably at least 25%, more preferably at least 75%, of the surfactant is an alcohol Ethoxylated linear chain primary. It is also preferred that the HLB (hydrophilic-lipophilic balance) of the surfactant be about 7 to about 13. Commercial products of use in the present invention include the Lutensol®TO series, oxo ethoxylated C13 alcohol, marketed by BASF, being especially suitable for use in the present invention Lutensol®TO7.

2. Auxiliary surfactants

The level of auxiliary surfactant in the compositions of the invention is preferably about 5% to about 70%, preferably from about 10% to about 60% and more preferably about 15% at approximately 55%, by weight of the composition. Surfactants Preferred auxiliaries for use in the present invention include nonionic surfactants of the ethoxylated / propoxylated fatty alcohol type  low foaming and non-ionic surfactants capable of acting as suds suppressors for more active surfactants of foam

2.1 Non-ionic surfactants of the fatty alcohol type ethoxylated / propoxylated

Fatty alcohols C 6 -C 18 ethoxylated / propoxylated are highly preferred surfactants for use as surfactants auxiliary, especially if they are soluble in water. Preferably mixed ethoxylated / propoxylated fatty alcohols have a alkyl chain length from about 8 to about 18, preferably from about 10 to about 14, carbon atoms, an average degree of ethoxylation of 3 to 15, preferably from about 4 to about 8, and a degree of propoxylation from about 1 to about 10, preferably from about 1 to about 4. The nonionic fatty alcohol type surfactants Preferred ethoxylated / propoxylated are Plurafac surfactants, marketed by BASF, especially those of the RA series, in particular Plurafac RA30.

2.2 Non-ionic surfactants of suppressor type of suds

Nonionic surfactants to use as soaps suppressants have a cloud point low. The expression "cloud point", in the present memory is a well known property of non-surfactants ionic which is that the surfactant becomes less soluble by increase the temperature, and the temperature at which the appearance of a second phase is called "point of cloudiness "(see Kirk Othmer, p. 360-362). Herein, a surfactant does not Ionic "low cloud point" is defined as a non-ionic surfactant system ingredient that has a point of cloudiness of less than 30 ° C, preferably less than about 20 ° C, and even more preferably less than approximately 10 ° C and most preferably less than approximately 7.5 ° C. The non-ionic surfactants of Typical low cloudiness include non-alkoxylated surfactants. ionic, especially ethoxylated derivatives of primary alcohol, and inverse block polymers of polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO). These nonionic low cloud point surfactants include also, for example, alcohol ethoxylated-propoxylated (e.g., Poly-Tergent® SLF18 from Olin Corporation) and poly (oxyalkylated alcohols) terminally protected with epoxy groups (e.g., the Poly-Tergent® SLF18B series of non-ionic surfactants from Olin Corporation, as described, for example, in US-A-5,576,281).

Other cloud point surfactants Low suitable are the suds suppressors polyoxyalkylated terminal protected with ether groups that They have the formula:

one

where R 1 is a hydrocarbon linear alkyl that has an average of about 7 to approximately 12 carbon atoms, R2 is a hydrocarbon linear alkyl of about 1 to about 4 atoms of carbon, R 3 is a linear alkyl hydrocarbon of about 1 to about 4 carbon atoms, x is a integer from about 1 to about 6, and is a integer from about 4 to about 15 and z is a integer from about 4 to about 25.

Other non-ionic surfactants Low cloudiness are the terminal polyoxyalkylated protected with ether groups that have the formula:

2

where R_ {I} is selected from group consisting of aliphatic hydrocarbon radicals or aromatic, substituted or unsubstituted, saturated or unsaturated, linear or branched that are approximately 7 to about 12 carbon atoms; R_ {II} can be the same or different and are selected, independently of each other, from the group consisting of C2 to C7 alkylene branched or linear in any given molecule; n is a number from 1 to about 30 and R_ {III} is selected from the group consisting in:

(i)

a substituted or unsubstituted heterocyclic ring of 4 to 8 elements containing 1 to 3 heteroatoms; Y

(ii)

aliphatic hydrocarbon radicals or aromatic, cyclic or acyclic, substituted or unsubstituted, saturated or unsaturated, linear or branched that have about 1 to about 30 carbon atoms;

(iii)

with the proviso that when R 2 is (ii) then or: (A) at least one of R 1 is different of C 2 -C 3 alkylene or (B) R 2 has 6 to 30 atoms of carbon and also with the condition that when R2 has 8 to 18 carbon atoms, R is different from C 1 alkyl - C_ {5}.

If suds suppressors are used, no ionic, these are preferably used at a level of about 5% to about 40%, preferably of about 10% to about 35% and more preferably of about 15% to about 25%, by weight of the composition.

3. Organic vehicles

Organic vehicles are preferably primary or secondary low molecular weight alcohols selected from the group consisting of: methanol, ethanol, propanol, isopropanol, glycerol, propylene glycol, ethylene glycol, 1,2-propanediol, sorbitol and mixtures thereof. If used, organic vehicles are used at a level of about 5% to about 40%, preferably of about 10% to about 35% and more preferably of about 15% to about 25%, by weight of the composition.

4. Dispersants and growth inhibitors crystalline

The function of the dispersant is to suspend the inorganic salts in the wash solution and minimize its deposition  on the dishes. Some dispersants can also act as crystal growth inhibitors.

Suitable for use in the present invention as dispersants are copolymers synthesized from Acrylic acid, maleic acid and methacrylic acid such as Acusol 480N, marketed by Rohm & Haas, and the polymers that contain carboxylate and sulphonate monomers such as Alcosperse polymers (marketed by Alco).

Crystal growth inhibitors Preferred for use in the present invention include acids organophosphonic. By organodiphosphonic acid is understood in the present memory an organodiphosphonic acid that does not contain nitrogen in its chemical structure. Therefore, this definition excludes organoaminophosphonates, which, without However, they can be included in the compositions of the invention as heavy metal ion sequestrant components.

The organodiphosphonic acid is preferably a C 1 -C 4 diphosphonic acid, plus preferably a C2 diphosphonic acid such as ethylene acid diphosphonic or most preferably an ethane acid 1-hydroxy-1,1-diphosphonic  (HEDP), and may be present partially or totally ionized, especially as a salt or complex.

5. Silicone type antifoaming agents

Suitable antifoaming agents may be selected from the group consisting of defoamers based on silicon, in particular antifoaming agents of the type conventional inorganic filler polydimethylsiloxane, especially anti-foaming agents of the polydimethylsiloxane type with silica filler as described in US-A-4,639,489 and US-A-3,455,839. These and others suitable antifoaming agents are marketed with the names Silcolapse 431 and Silicone EP 6508 by ICI United States Inc., Wilmington, Delaware, US-A .; Rhodosil 454 by Rhone-Poulenc Chemical Co., Monmouth Junction, New Jersey, USA; and Silkonol AK 100 by Wacker-Chemie G.m.b.H., Munich, Federal Republic of Germany.

6. Moisturizers

The humectant is a substance that can capture or emit moisture to your environment based on relative humidity surrounding. The humectants suitable for use herein invention include hydrophilic non-aqueous organic solvents including glycols and polyhydric alcohols, for example sorbitol, glycerol, dipropylene glycol and mixtures thereof.

In the present invention the rinse composition is part of a multiphase unit dose product, preferably a two-compartment water-soluble bag, wherein one of the phases comprises a detergent composition for the main wash. Preferred compositions and manufacturing methods for unit dose embodiments are described in WO 02/42408. Any water-soluble film-forming polymer that is compatible with the compositions of the invention and that allows the composition to be supplied to the rinse cycle can be used in the unit dose. The film should remain intact during the wash cycle and dissolve only at the beginning or during the rinse cycle. This can be achieved by modifying the thickness of the film and / or the solubility of the film material. The solubility of the film-like material can be delayed by, for example, crosslinking of the film as described in WO 02 / 102,955 on pages 17 and 18. Other water soluble films designed to be released in the rinse are described. in
4,765,916.

Examples

The compositions of the following examples are express as a percentage by weight of the composition.

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A load was placed in a GE 500 dishwasher which included 3 glasses of wine, 1 glass with drawing, 1 glass Libby, 1 large plastic jar, 1 black plate, 1 large plastic box for food, 1 small plastic box for food and 1 ladle of metal to serve. Water temperature stabilized at 37-50ºC through a tank system before pump it to the dishwasher. The total washing process in the dishwasher lasted approximately 60 minutes ("normal" cycle) and the heating option in the drying cycle was switched off. Be they used 50 grams of powder detergent from the Cascade line (marketed by Procter and Gamble) for the main wash and 2 ml of the rinse aid composition of the Example 1 to the rinse cycle from the auxiliary tank of cleared up. After the end of the drying cycle, the items are kept in the dishwasher for 5 minutes and then Were evaluated. Full drying was observed and the items were not they presented watermarks and had a strong shine. Results Similar can be observed when using compositions 2 to 7.

Claims (6)

1. A multiphase unit dose product that it comprises at least two phases, wherein one phase comprises a concentrated rinse aid composition practically no aqueous for heat-free drying of plastic and other objects dishwashing articles, the composition comprising less than 20% by weight of water and at least 20% by weight of one or more superhumidifying surfactants, wherein the surfactant super moisturizer is selected from the group consisting of: i) polyoxyalkylene siloxanes wherein the residue of poly (oxide of alkylene) has the general formula (EO) n (PO) m where n is at least 3 and greater than m; ii) nonionic ethoxylated alcohols having a average of 4 to 10 moles of EO per mole of alcohol and a length of average chain of 6 to 15 carbon atoms; iii) and mixtures of themselves, and where one of the phases comprises a composition detergent for the main wash and a means to release the concentrated rinse aid composition practically no aqueous to the rinse cycle of a dishwasher. 2. A unit dose product according to the claim 1, wherein the rinse aid composition practically non-aqueous concentrate also comprises a surfactant non-superhumidifying auxiliary 3. A unit dose product according to the claim 2, wherein the superhumidifying surfactant comprises  at least 10% by weight of the type surfactant composition siloxane and where the superhumidifying surfactant and the Auxiliary surfactant are in a ratio of 1: 1 to 1: 5. 4. A unit dose product according to the claim 2, wherein the auxiliary surfactant is a suppressor of the soaps and the superhumidifying surfactant and the Auxiliary surfactant are in a ratio of 5: 1 to 1: 1. 5. A unit dose product according to any of the preceding claims, wherein the concentrated rinse aid composition practically no aqueous also comprises one or more additional ingredients selected from the group consisting of: organic vehicles, antifoaming agents, humectants, dispersants, inhibitors of crystalline growth and mixtures thereof. 6. A unit dose product according to any of the preceding claims, wherein the concentrated rinse aid composition practically no aqueous has a pH of 6 to 8 measured in a 1% aqueous solution in weight at 20 ° C.