RU2547257C2 - Laundry detergents - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to laundry detergents. Disclosed is a laundry detergent containing a granular foam control composition and an anionic surfactant, wherein the granular foam control composition contains a foam control agent, a composition of organic additives, a water-soluble inorganic carrier in the form of particles and a charged cationic polymer. The foam control agent contains liquid polydiorganosiloxane liquid, hydrophobic filler and an organosilicon resin. The invention also discloses a fabric cleaning method, a method of saving water during laundry and a method of saving time during laundry using the disclosed detergent.

EFFECT: disclosed detergent composition provides a satisfactory foam volume during the washing stage and a considerably low foam volume after rinsing once.

12 cl, 2 tbl, 9 ex

Description

Cross reference to related applications

This application claims the priority of PCT Chinese Application No. PCT / CN 2010/002009, filed December 10, 2010.

FIELD OF THE INVENTION

The present invention relates to detergents for washing. Specifically, the present invention relates to laundry detergents comprising granular foam control compositions containing silicones.

State of the art

Laundry detergents that contain surfactants and typically anionic surfactants for cleaning fabrics such as clothing have been known for many years. Detergents for washing usually create foam in the process of their use, including use for hand washing. During hand-washing of clothes and fabrics in which the user is closely associated with the washing process, a large volume of foam is initially desirable as it indicates to the user that a sufficient amount of surfactant is present while working and cleaning the fabrics. However, during a rinse cycle, a typical user of a hand wash detergent is inclined to believe that if foam is still present, then there is a surfactant residue that remains on the clothes and therefore believes that the clothes are not yet “clean”. Thus, it is usually rinsed several times, until the foam is not visible when rinsing.

Thus, while a large volume of foam is desirable during cleaning, it is paradoxically undesirable during rinsing. It usually takes 3-6 rinses to remove such foam to satisfy the person who launders the wash. This adds a large amount of water, which is used daily for rinsing all over the world - typically about 5-10 tons of water per year per family for hand washing in countries such as India, China, etc. Since water is often a limited resource, especially in countries where it is washed by hand, the use of rinse water reduces the amount of water available for other possible uses, such as irrigation, drinking, bathing, etc. Depending on the location and local practice, there may be additional energy costs or labor costs associated with rinsing, both reusable and with so much water.

It has been found that, in fact, fewer rinses can sufficiently remove surfactants and, therefore, many rinses are not necessary. A foaming suppressant that is selectively active during rinsing can eliminate undesirable excessive foam during rinsing and thereby change the consumer's perception of the adequacy and effectiveness of one rinse, thereby saving water and the effort involved in repeated rinsing.

Foam suppressants are well known, for example, detergents for automatic washing dishes and detergents for washing for front-loading washing machines. Examples of foaming suppressants are disclosed, for example, in EP 1075683A, EP 1070526A, US 7632890 B and EP 210731 A. However, since typical foaming suppressants do not distinguish between washing and rinsing conditions, they do not solve the problem of providing foam during washing and only reduce foam during rinse. In particular, in a hand-washing situation, consumers are accustomed to seeing foam during washing, and if there is no foam, then consumers believe that the detergent for washing does not contain enough surfactant to meet their expectations. PCT Publication WO 2007/028773 A1, Dow Corning, published October 9, 2003, relates to a solid composition for the release of active silicone, which contains a cationic polymer, an active silicone ingredient and optionally a polymer thickener and carrier. The cationic polymer is a homopolymer or copolymer derived from monoethylenically unsaturated monomers. The thickener is a polyacrylate, polysaccharide, polymer gum and / or their derivative. Granular encapsulated compositions can be prepared using a solid silicone-releasing composition as a component in a laundry detergent in the form of a powder, tablet or bar. It is of interest for the delivery of silicone ingredients in the rinse cycle in the strips operation.

PCT publication WO 2009/103576, Unilever, published August 20, 2009, discloses a particle that contains a silicone-based beneficial agent and a charged water-soluble polymer film-forming material, preferably polyvinyl alcohol. The film remains substantially intact in the presence of a surfactant and is destroyed when the concentration of the surfactant is sufficiently reduced, thereby releasing the beneficial agent. This particle can be included in detergents for washing, intended for washing fabrics.

US publication 2005/176598, Catharine et al., Published August 11, 2005, discloses a controlled release delivery system that can be incorporated into laundry detergent for heat-activated delivery of the active agent. The delivery system is a nanosphere containing a cationic conditioning agent, which in combination with a cationic charge enhances the retention of spheres on the surface.

Thus, a detergent composition is desired that provides a satisfactory foam volume during the washing step and significantly reduces the foam volume after a single rinse process. There are a number of disclosures about a detergent composition that selectively reduces foam at the rinse stage, but none of them provide an equally good foam control profile during the washing and rinsing steps to the extent provided by the present invention.

SUMMARY OF THE INVENTION

The present invention relates to a washing detergent containing a granular composition for controlling foaming and an anionic surfactant, wherein said granular composition for controlling foaming contains a foaming control agent containing a polydiorganosiloxane liquid, a hydrophobic filler, and wherein said granular composition for controlling foaming also contains a composition of organic additives, a water-soluble inorganic carrier in ph Particle and charged polymer. The present invention also relates to a method for cleaning fabrics, a method for saving water when washing a fabric, and a method for saving time when washing a fabric.

This washing detergent can provide the expected level of cleaning, as evidenced by the desired amount of foam when washing, and also helps to convince users to reduce the number of rinses and thereby save water, effort, resources, etc. with a significant reduction in foam volume with a single rinse. Not intending to be bound by theory, it is believed that the anionic surfactants in the laundry detergent coacervate with a granular foam control composition containing a foam control agent, and such coacervate remains intact during washing and only selectively breaks down during rinsing when surfactant level decreases.

DETAILED DESCRIPTION OF THE INVENTION

All temperatures in this application are given in degrees Celsius (° C), unless otherwise indicated. As used in this application, the term “comprising” means that other steps, ingredients, elements, etc. that do not adversely affect the end result can be added. This term covers the terms “consisting of” and “consisting essentially of”. All conditions in this application are 20 ° C and atmospheric pressure, unless otherwise indicated. Unless otherwise indicated, the ingredients and equipment in this application are believed to be widely available from various suppliers and sources worldwide. All polymer molecular weights are weight average molecular weights unless otherwise indicated.

As used in this application, “foam” indicates a nonequilibrium dispersion of gas bubbles in a relatively small volume of liquid. Terms like “foam” and “soap foam” can be used interchangeably in this application.

The present invention relates to a washing detergent containing a granular composition for controlling foaming and an anionic surfactant, wherein said granular composition for controlling foaming contains a foaming control agent comprising a polydiorganosiloxane liquid, a hydrophobic filler and said granular composition for controlling foaming a composition of organic additives, a water-soluble inorganic carrier in the form of a part q and a charged polymer. The present invention also relates to a method for cleaning fabrics, a method for saving water when washing a fabric, and a method for saving time when washing a fabric.

This detergent for washing can be obtained by combining a granular composition for controlling foaming with an existing laundry detergent containing anionic surfactants.

Granular composition for controlling foaming

Granular foam control compositions are typically added to laundry detergents at a level of from about 0.1%, 0.2%, 0.5% to about 1.0%, 10% by weight. The granular foam control compositions of the present invention have been found to have minimal effect on foam during washing, for example less than about 35% reduction in foam, or, as defined later in this application, have a foam index for washing at least at least about 65%, with a significant reduction in foam during the first rinse, for example, more than about 50% reduction in foam, or, as defined below in this application, have a foaming index when rinsing less than about 50%. This has been found to be confirmed by hand washing, as well as by using semi-automatic machines.

Foam Control Agent

The foam control agent comprises a polydiorganosiloxane liquid, a hydrophobic filler, and optionally an organosilicon resin. The polydiorganosiloxane liquid may be a polydiorganosiloxane liquid containing units of the formula:

,

,

where each R group, which may be the same or different, is selected from an alkyl group containing from 1 to 36 carbon atoms, or an aryl group or an aralkyl group containing from 1 to 36 carbon atoms, the average number of carbon atoms in R groups is, by at least 1.3. In one embodiment, the polydiorganosiloxane liquid preferably contains no more than 5 mol.% Of branched units, such as RSiO _3/2 units, or cross-linking sites, most preferably less than 2 mol.% Of branched units. The average number of carbon atoms in the R groups is preferably at least 1.3 and more preferably at least 2.0, most preferably at least 2.5, if the R groups do not include aryl or aralkyl groups . The polydiorganosiloxane liquid is free of non-silicone polymer chains, such as polyester chains.

One preferred example of a polydiorganosiloxane liquid is polysiloxane containing at least 10% diorganosiloxane units of the formula

and up to 90% of diorganosiloxane units of the formula

,

,

where X is a divalent aliphatic organic group bonded to silicon via a carbon atom; Ph is an aromatic group; Y means an alkyl group containing from 1 to 4 carbon atoms; and Y 'is an aliphatic hydrocarbon group containing from 1 to 24 carbon atoms, as described in EP 1075864. Diorganosiloxane units containing an —X-Ph group preferably contain from 5 to 60% diorganosiloxane units in a liquid. Group X is preferably a divalent alkylene group containing from 2, 4 to 10 carbon atoms, but may alternatively contain an ester bond between two alkylene groups or between an alkylene group and -Ph or may contain an ester bond.

In one embodiment, Ph represents a phenyl group, but may be substituted, for example, by one or more methyl, methoxy, hydroxy or chloro groups, or two substituents on the Ph group may together form a divalent alkylene group, or may together form an aromatic ring, resulting in getting a combination with a Ph group, for example a naphthalene group. In another embodiment, the X-Ph group is 2-phenylpropyl —CH ₂ —CH (CH ₃ ) —C ₆ H ₅ . Group Y may be methyl, but may also be ethyl, propyl or butyl. The group Y 'has from 1 or 2 to 16 or 18 carbon atoms, for example, represents ethyl, methyl, propyl, isobutyl or hexyl. Mixtures of Y 'alkyl groups can be used, for example ethyl and methyl, or a mixture of dodecyl and tetradecyl. Other groups may be present, for example, haloalkyl groups such as chloropropyl, acyloxyalkyl or alkoxyalkyl groups, or aromatic groups such as phenyl bonded directly to Si.

The polysiloxane liquid containing —X-Ph groups may be a substantially linear siloxane polymer or may have some branching, for example branching in the siloxane chain in the presence of certain trifunctional siloxane units, or branching into multivalent, for example divalent or trivalent, organic or organosilicon moieties, binding polymer chains as described in EP 1075684 A.

An alternative example of a preferred polydiorganosiloxane liquid is polysiloxane comprising 50-100% diorganosiloxane units of the formula

and optionally up to 50% diorganosiloxane units of the formula

,

,

where Y is an alkyl group containing from 1 to 4 carbon atoms, and Z is an alkyl group containing from 6 to 18 carbon atoms. The Y groups in such a polydiorganosiloxane are preferably methyl or ethyl. The alkyl group Z may preferably contain from 6 to 12 or 14 carbon atoms, for example octyl, hexyl, heptyl, decyl or dodecyl, or a mixture of dodecyl and tetradecyl.

In one embodiment, the amount of siloxane units (DP, polymerization degree) in the middle polysiloxane liquid molecule of any of the above types is at least 5, more preferably from about 5, 10 and 20 to about 200, 1000 and 5000. The polysiloxane end groups may be any of these traditionally present in siloxanes, for example trimethylsilyl end groups.

A polydiorganosiloxane liquid containing —X-Ph groups or a polydiorganosiloxane liquid containing —Z groups is preferably present as at least 80%, 95% by weight of the polysiloxane liquid content of the foam control composition, more preferably 100% polysiloxane liquid.

The polydiorganosiloxane liquid may alternatively be a polydiorganosiloxane in which the organic groups are essentially all alkyl groups containing from 2 to 4 carbon atoms, for example polydiethylsiloxane.

The foam control agent contains a hydrophobic filler dispersed in a polydiorganosiloxane liquid. Hydrophobic fillers for foaming control agents are well known and are particulate materials that are solid at 100 ° C, such as silica, preferably with a surface area measured by BET measurement of at least 50 m ² / g, dioxide titanium, crushed quartz, alumina, aluminosilicate, zinc oxide, magnesium oxide, a salt of aliphatic carboxylic acids, a reaction product of an isocyanate with an amine, for example cyclohexylamine, or an alkyl amide such as ethylene bis stearamide or methylene bis stearam id Mixtures of two or more of them may be used.

Some of the fillers mentioned above are not hydrophobic in nature, but can be used if they are hydrophobic. This can be done either in situ (i.e., when dispersed in a polysiloxane liquid), or by pre-treating the filler before mixing with the polysiloxane liquid. A preferred filler is silica, which is made hydrophobic. Preferred silica materials are those obtained by heating, for example fumed silica, or by precipitation. The silica filler may, for example, have an average particle size of from 0.5, 2 and 5 to about 25, 30 and 50 microns. It can be made hydrophobic by treatment with a fatty acid, but is preferably hydrophobic prepared using methyl substituted organosilicon materials such as dimethylsiloxane polymers which are end-blocked with silanol or alkoxy kremniysvyazannymi, geksametildisilazanovymi, geksametildisiloksanovymi or organosilicon resins containing (CH _{3) 3} SiO _1/2 groups and silanol groups. Hydrophobicity is generally imparted at a temperature of at least 100 ° C. Mixtures of fillers can be used, for example a highly hydrophobic silica filler, commercially available under the name Sipemat D10 from Evonik together with partially hydrophobic silica, for example under the name Aerosil R972 from Evonik.

The amount of hydrophobic filler in the foam control agent according to the present invention is preferably 0.5-50% by weight based on the polysiloxane liquid, more preferably from 1 to 10 or 15% and most preferably from 2 to 8% by weight.

The foaming control agent optionally contains an organosilicon resin that is bound to a polydiorganosiloxane liquid. Such an organosilicon resin can improve the control of foaming of polysiloxane liquid. This is especially true for polysiloxane fluids containing -X-Ph groups, as described in EP 1075684 A, and also for polysiloxane fluids containing -Z groups. In such polysiloxane fluids, the resin modifies the surface properties of the fluid.

The organosilicon resin is generally a non-linear siloxane resin and preferably consists of siloxane units of the formula R'aSiO _{4-a / 2} , where R 'is a hydroxyl, hydrocarbon or hydrocarbonoxy group and where "a" has an average value of from 0.5 to 2, four. It preferably consists of monovalent trihydrocarbonyloxy (M) groups of the formula R ″ ₃ SiO _1/2 and tetrafunctional (Q) groups SiO _4/2 , where R ″ means a monovalent hydrocarbon group. The quantitative ratio of groups M and groups Q is preferably in the range from 0.4: 1 to 2.5: 1 (equivalent to the value of a in the formula R ' _a SiO _{4-a / 2} from 0.86 to 2.15), more preferably from 0.4: 1 to 1.1: 1 and most preferably from 0.5: 1 to 0.8: 1 (equivalent to a = 1.0 to a = 1.33).

The organosilicon resin is preferably a solid at room temperature. The molecular weight of the resin can be increased by condensation, for example by heating in the presence of a base. The base may be, for example, an aqueous or alcoholic solution of potassium hydroxide or sodium hydroxide, for example, a solution in methanol or propanol. A resin containing M groups, trivalent R 'SiO _3/2 units (T), and Q units can be used alternatively, or up to 20% of the units in the organosilicon resin can be divalent R _{2 2} SiO _2/2 units. The R ″ group is preferably an alkyl group containing from 1 to 6 carbon atoms, for example methyl or ethyl, or may be phenyl. It is particularly preferred that at least 80%, most preferably substantially all, of the R ”groups present are methyl groups. The resin may be a trimethyl terminal resin.

The silicone resin is preferably present in the foam control agent at 1-50% by weight based on the polysiloxane liquid, in particular 2-30% and most preferably 4-15%. The silicone resin may be soluble or insoluble in the polysiloxane liquid. If the resin is insoluble in the polysiloxane liquid, the average particle size of the resin may, for example, be from about 0.5 and 2 to about 50 and 400 microns.

The granular foam control agent of the present invention may contain additional ingredients, such as a density regulator, a color preservative such as maleate or fumarate, for example bis (2-methoxy-1-ethyl) maleate or diallyl maleate, acetylene alcohol, for example methyl butynol or cyclooctadiene, a thickening agent such as carboxymethyl cellulose, polyvinyl alcohol or hydrophilic or partially hydrophobic fumed silica, or a coloring agent, such as a pigment or dye.

The composition of organic additives

An organic additive with a melting point of from about 45 ° C to about 100 ° C is miscible with a polydiorganosiloxane liquid. By “miscible” is meant that materials in the liquid phase (ie, molten if necessary) are mixed in the proportions in which they are present in the composition for controlling foaming, without showing phase separation. This can be judged by the transparency of the liquid mixture in the absence of any filler or resin. If the liquids are miscible, the mixture is transparent and remains as one phase. If the liquids are immiscible, the mixture is opaque and is divided into two phases upon settling. Organic supplementation increases the effectiveness of foam control. We have found that additives with a melting point of at least about 45 ° C are effective in increasing the effectiveness of the foaming control during rinsing.

The organic additive contains a polyol ester, which is a polyol partially or fully esterified with carboxylate groups, each of which contains from 7 to 36 carbon atoms. The polyol ester is preferably a glycerol ester or an ester of a higher polyol such as pentaerythritol or sorbitol. The polyol ester is preferably a monocarboxylate or polycarboxylate (e.g., dicarboxylate, tricarboxylate or tetracarboxylate) in which each carboxylate group contains from 18 to 22 carbon atoms. Such polyol carboxylates typically have a melting point of at least 45 ° C. The polyol ester can be a glycol diester, such as ethylene glycol or propylene glycol, preferably with a carboxylic acid containing at least 14, 18 to 22 carbon atoms, for example ethylene glycol distearate. Examples of glycerol esters include glycerol tristearate and saturated carboxylic acid glycerol esters containing 20 or 22 carbon atoms, such as a material with a melting point of approximately 54 ° C, commercially available under the trade name Synchrowax HRC from Croda, believed to be mainly triglyceride C ₂₂ fatty acids with some C ₂₀ and C ₁₈ chains. Alternative acceptable polyol esters are pentaerythritol esters such as pentaerythritol tetrabehenate and pentaerythritol tetrastearate.

The polyol ester may contain fatty acids with different chain lengths, which is common in natural products. The organic additive may be a mixture of polyol esters, for example a mixture of esters containing various carboxylate groups, for example, tripalmitate glycerol and tristearate glycerol, or tristearate glycerol and Synchrowax HRC, or ethylene glycol distearate and Synchrowax HRC.

The organic additive may also contain a more polar polyol ester. In one embodiment, polar polyol esters include partially esterified polyols, including monoesters or diesters of glycerol with a carboxylic acid containing from 8 to 30 carbon atoms, for example, monostearate glycerol, monolaurate glycerol, distearate glycerol, or monobeganate glycerol. Mixtures of glycerol monoesters and diesters can be used. Partial esters of other polyols can also be used, for example, propylene glycol monopalmitate, monostearate sorbitan and ethylene glycol monostearate.

An organic additive may be present in the granular composition to control foaming from about 10%, 20% to about 100%, 120% and 200% by weight of the polydiorganosiloxane liquid.

Particulate Water-Soluble Inorganic Carrier

The foaming control agent is coated with particulate water-soluble inorganic carriers to form a granular foam control composition that can be easily incorporated into the laundry detergent. Examples of particulate water-soluble inorganic carriers are phosphates, for example, powdered or granular sodium tripolyphosphate, sodium sulfate, sodium carbonate, for example anhydrous sodium carbonate or sodium carbonate monohydrate, sodium silicate, sodium citrate, sodium acetate, sodium sexvicarbonate, sodium bicarbonate, and mixtures thereof. The particle size of the water-soluble inorganic carrier is preferably in the range of from about 1 to about 40 microns, more preferably from 1 to 20 or 30 microns.

We have found that the use of a water-soluble inorganic particulate carrier markedly increases the effectiveness of the granular foam control composition of the present invention compared to a water-insoluble carrier.

Charged polymer

As used in this application, the charged polymer may be a cationic polymer, an amphoteric polymer, or mixtures thereof. Amphoteric polymers in accordance with the present invention will also have a total cationic charge, that is, the total cationic charges on these polymers will exceed the total anionic charge. The charge density of the charged polymer is in the range of from about 0.05, 0.5 and 2.5 to about 7, 12 and 23 milliequivalents / g (hereinafter, briefly “meq / g”). Charge density is calculated by dividing the total charge by a repeating unit by the molecular weight of the repeating unit. Positive charges can be on the polymer framework or on the side chains of the polymers. For polymers with amine monomers, the charge density depends on the pH of the carrier. For these polymers, charge density is measured at pH 7.

The weighted average molecular weight of the charged polymer will generally be from about 80,000, about 150,000, about 200,000 to about 3,000,000, about 4,000,000, as determined by size exclusion chromatography relative to polyethylene oxide standards with RI detection. The mobile phase used in the chromatography is a solution of 20% methanol in 0.4 M MEA, 0.1 M NaNO ₃ , 3% acetic acid on a Waters Linear Ultrahdyrogel, 2 column in series. Columns and detectors are stored at 40 ° C. The flow rate was set to 0.5 ml / min.

For a useful charged polymer in accordance with the present invention, the molecular weight and charge density can act to “compensate” each other. Polymers with a lower charge density will work, provided that their molecular weight is high enough, and polymers with a lower molecular weight will work, provided that their charge density is high enough. So here the optimal cationicity parameter appears, where the cationicity parameter is defined as the molecular mass of the product · charge density / 1000 (MW · CD / 1000). Preferred charged polymers have a cationicity parameter of from about 50, about 100, about 150 to about 50,000, about 70,000, about 90,000 meq · Da / g.

Non-limiting examples of a charged polymer are cationic or amphoteric polysaccharides, proteins, and synthetic polymers.

but. Cationic Polysaccharides:

Cationic polysaccharides include, but are not limited to, cationic cellulose derivatives, cationic guar gum derivatives, chitosan and derivatives and cationic starches. Cationic polysaccharides have a molecular weight of from about 50,000 to about 2 million, preferably from about 100,000 to about 1,500,000.

One group of preferred cationic polysaccharides is shown in structural formula I as follows:

,

,

,where R ¹ , R ² , R ³ each independently represents H, C1-24 alkyl (linear or branched),

,

или их смеси, где Z представляет собой водорастворимый анион, предпочтительно хлорид, бромид йодид, гидроксид, фосфат сульфат, метил сульфат и ацетат; R⁵ выбран из H, или C1-C6 алкила или их смесей; R⁷, R⁸ и R⁹ выбраны из H или C1-C28 алкила, бензила или замещенного бензила или их смесей;where n is from about 0 to about 10; R ^x represents H, C1-24 alkyl (linear or branched) or

or mixtures thereof, where Z is a water-soluble anion, preferably chloride, bromide iodide, hydroxide, phosphate sulfate, methyl sulfate and acetate; R ^{5 is} selected from H, or C1-C6 alkyl, or mixtures thereof; R ⁷ , R ⁸ and R ⁹ are selected from H or C1-C28 alkyl, benzyl or substituted benzyl, or mixtures thereof;

R ⁴ represents H or - (P) mH or mixtures thereof; where P is a repeating unit of the additive polymer formed by the cationic monomer. In one embodiment, the cationic monomer is selected from methacrylamidotrimethylammonium chloride, dimethyldiallylammonium having the formula

,

,

which results in a polymer or copolymer having units of the formula

,

,

where Z 'is a water-soluble anion, preferably chloride, bromide iodide, hydroxide, phosphate sulfate, methyl sulfate and acetate, or mixtures thereof, and m is from about 1 to about 100.

The alkyl substitution on the saccharide rings of the polymer is in the range of from about 0.01% to 5% per sugar unit, more preferably from about 0.05% to 2% per glucose unit, of the polymer material.

Preferred cationic polysaccharides include cationic hydroxyalkyl celluloses. Examples of cationic hydroxyalkyl celluloses include INCI Polyquaternium 10, for example, which are sold under the trade names Ucare Polymer JR 30M, JR 400, JR 125, LR 400 and LK 400 polymers; Polyquarter 67, which is sold under the trade name Softcat SK TM, all of which are available from Amerchol Corporation Edgewater NJ; and Polyquatern 4, available under the trade names Celquat H200 and Celquat L-200 from National Starch and Chemical Company, Bridgewater, NJ. Other preferred polysaccharides include hydroxyethyl cellulose or hydroxypropyl cellulose, quaternized glycidyl C12-C22 alkyl dimethyl ammonium chloride. Examples of such polysaccharides include polymers with the names INCI Polyquaternium 24, which are sold under the trade name Quaternium LM 200, PG-hydroxyethyl cellulose lauryl dimonium chloride, which are sold under the trade name Crodacel LM, PG-hydroxyethyl cellulose cocodimonium chloride, which are sold under the trade name Qd M cro β-hydroxyethyl cellulose stearyldimonium chloride, which is sold under the trade name Crodacel QS, and alkyldimethylammonium hydroxypropyloxyethyl cellulose.

In one embodiment of the invention, the cationic polymer comprises cationic starch. They are described in D.V. Solarek in Modified Starches, Properties and Uses, published by CRC Press (1986) and US Pat. No. 7,135,451, col. 2, line 33 - count. 4, line 67. In another embodiment, the cationic starch in accordance with the present invention contains amylose at a level of from about 0% to about 70% by weight of cationic starch. In yet another embodiment, if the cationic starch contains cationic corn starch, the cationic starch contains from about 25% to about 30% amylose by weight of cationic starch. In the above embodiments, other polymers containing amylopectin may be present in said cationic starch for the remaining percentage.

A third group of preferred polysaccharides is cationic galactomannans, such as cationic guar gums or cationic locust bean gum. Examples of cationic guar gums are quaternary ammonium derivatives of hydroxypropyl guar, which are sold under the trade names Jaguar C13 and Jaguar Excel available from Rhodia, Inc, Cranburry NJ and N-Hance, Aqualon, Wilmington, DE.

b. Synthetic cationic polymers

Synthetic cationic polymers in general and a process for their preparation are known in the literature. For example, a detailed description of cationic polymers can be found in an article by M. Fred Hoover published in Journal of Macromolecular Science-Chemistry, A4 (6), p. 1327-1417, October, 1970. The full disclosure of the Hoover article is incorporated herein by reference. Other suitable cationic polymers are those used as retention aids in papermaking. They are described in Pulp and Paper, Chemistry and Chemical Technology Volume III, edited by James Casey (1981). The molecular weight of such polymers is in the range of from about 80,000 to about 4,000,000 Da. Synthetic cationic polymers in accordance with the present invention will be better understood in the light of Hoover's article and Casey's book, this description and examples given in this application.

i. Additive polymers

Synthetic polymers include, but are not limited to, synthetic additive polymers of the general structure

,

,

where R ¹ , R ² and Z are defined in this application below. Preferably, the linear polymer units are formed from linearly polymerizable monomers. Linearly polymerizable monomers are defined in this application as monomers that under standard polymerization conditions result in a linear or branched polymer chain or alternatively that linearly extend the polymerization. The linearly polymerizable monomers in accordance with the present invention have the formula:

;

;

however, experts in this field recognize that many useful linear monomer units are introduced indirectly, in particular vinylamine units, vinyl alcohol units, rather than linearly polymerizable monomers. For example, vinyl acetate monomers, when incorporated into a framework, are hydrolyzed to form vinyl alcohol units. For the purposes of the present invention, linear polymer units can be directly introduced, for example, via linearly polymerizable units or indirectly, for example, through a precursor, as is the case with vinyl alcohol described herein above.

Each R ¹ independently represents hydrogen, C1-C12 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, -ORa, or -C (O) ORa, where Ra is selected from hydrogen and C1-C24 alkyl and mixtures thereof. Preferably, R1 is hydrogen, C1-C4 alkyl, —ORa, or —C (O) ORa.

Each R ² independently represents hydrogen, hydroxyl, halogen, C1-C12 alkyl, -ORa, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocycle, heterocycle, and mixtures thereof. Preferred R ² is hydrogen, C 1 -C ⁴ alkyl, and mixtures thereof.

Each Z independently represents hydrogen, halogen; linear or branched C1-C30 alkyl, nitrile, N (R ³ ) ₂ —C (O) N (R ³ ) ₂ , —NHCHO (formamide); -OR ³ , -O (CH ₂ ) _n N (R ³ ) ₂ , -O (CH ₂ ) _n N + (R ³ ) _3X- , -C (O) OR ⁴ ; -C (O) N- (R ³ ) ₂ , -C (O) O (CH ₂ ) _n N (R ³ ) ₂ , -C (O) O (CH ₂ ) _n N + (R ³ ) _3X , OCO (CH ₂ ) _n N (R ³ ) ₂ , -OCO (CH ₂ ) _n N + (R ³ ) _3X- , -C (O) NH (CH ₂ ) _n N (R ³ ) ₂ , C (O) NH (CH ₂ ) _n N + (R ³ ) _3X- , - (CH ₂ ) _n N (R ³ ) ₂ , - (CH ₂ ) _n N + (R ³ ) _3X- ,

each R ³ independently represents hydrogen, C1-C24 alkyl, C2-C8 hydroxyalkyl, benzyl; substituted benzyl and mixtures thereof;

,each R ⁴ independently represents hydrogen or C1-C24 alkyl and

,

X is a water soluble anion; index n is from 1 to 6.

R ⁵ independently represents hydrogen, C1-C6 alkyl, and mixtures thereof.

Z may also be selected from a non-aromatic nitrogen-containing heterocycle containing a quaternary ammonium ion, a heterocycle containing an N-oxide fragment, an aromatic nitrogen-containing heterocycle, where one or more nitrogen atoms are quaternized; aromatic nitrogen-containing heterocycle, where at least one nitrogen atom is an N-oxide; or mixtures thereof. Non-limiting examples of addition polymerizable monomers containing a heterocyclic Z unit include 1-vinyl-2-pyrrolidinone, 1-vinylimidazole, quaternized vinyl imidazole, 2-vinyl-1,3-dioxolane, 4-vinyl-1-cyclohexene1,2-epoxide and 2-vinylpyridine, 2-vinylpyridine N-oxide, 4-vinylpyridine 4-vinylpyridine N-oxide.

A non-limiting example of the Z unit which can be obtained to form a cationic charge in situ is the —NHCHO unit, formamide. The formulator may produce a polymer or copolymer containing formamide units, some of which are then hydrolyzed to form vinyl amine equivalents.

The polymers and copolymers in accordance with the present invention include Z units that have a cationic charge or result in a cationic charge forming unit in situ. When the copolymers in accordance with the present invention contain more than one Z unit, for example, Z1, Z2, ... Zn units, at least about 1% of the monomers that contain the copolymers will contain a cationic unit.

The polymers or copolymers in accordance with the present invention may include one or more cyclic polymer units, which are obtained from cyclically polymerizable monomers. Cyclically polymerizable monomers are defined in this application as monomers, which under standard polymerization conditions lead to the formation of a cyclic polymer residue, and also serve to propagate linear polymerization. Preferred cyclically polymerizable monomers in accordance with the present invention have the formula

,

,

where each R ⁴ independently represents an olefin-containing unit capable of propagating polymerization in addition to the formation of a cyclic residue with an adjacent R ⁴ unit; R ⁵ is C1-C12 linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a water soluble anion.

Non-limiting examples of R ⁴ units include allyl and alkyl substituted allyl units. Preferably, the resulting cyclic residue is a six-membered ring containing a quaternary nitrogen atom.

R ^{5 is} preferably C1-C4 alkyl, preferably methyl.

An example of a cyclically polymerizable monomer is dimethyldiallylammonium having the formula:

,

,

resulting in a polymer or copolymer having units of the formula:

,

,

where preferably the z index is from about 10 to about 50,000.

Non-limiting examples of preferred polymers in accordance with the present invention include copolymers derived from one or more cationic monomers selected from the group consisting of

N, N-dialkylaminoalkylmethacrylate, N, N-dialkylaminoalkylacrylate, N, N-dialkylaminoalkylacrylate dialkylaminoalkylmethacrylamide vinylamine and its derivatives, allylamine and its derivatives, vinylimidazole, quaternized vinylimidazole and diallyldialkylammonium chloride and combinations thereof.

Optionally, the second monomer is selected from the group consisting of acrylamide, N, N-dialkyl acrylamide, methacrylamide, N, N-dialkyl methacrylamide, C1-C12 alkyl acrylate, C1-C12 hydroxyalkyl acrylate, polyalkylene glycol acrylate, C1-C12 alkyl methacrylate, C1-C12 alkyl methacrylate, C1-C12 alkyl vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ether, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole and derivatives, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, st rolsulfonovoy acid akrilamidopropilmetan sulfonic acid (AMPS) and salts thereof, and combinations thereof.

The polymer may optionally be crosslinked. Crosslinking monomers include, but are not limited to, ethylene glycol diacrylate, divinylbenzene, and butadiene.

Preferred cationic monomers include N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate (DMAM), [2- (methacryloyamino) ethyl] trimethylammonium chloride (QDMAM), N, N-dimethylaminopropylacrylamide (DMAPA), N, N-DMDMA ), acrylamidopropyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride (MARTAS), quaternized vinylimidazole and diallyldimethylammonium chloride and their derivatives.

Preferred second monomers include acrylamide, N, N-dimethylacrylamide, C1-C4 alkyl acrylate, C1-C4 hydroxyalkyl acrylate, vinyl formamide, vinyl acetate and vinyl alcohol. The most preferred nonionic monomers are acrylamide, hydroxyethyl acrylate (HEA), hydroxypropyl acrylate and their derivative.

The most preferred synthetic polymers are poly (acrylamide-co-diallyldimethylammonium chloride), poly (acrylamide-methacrylamidopropyltrimethylammonium chloride), poly (acrylamide-co-N, N-dimethylaminoethylmethacrylate), poly (acrylamide-co-N, n-ethylmethyl) (hydroxyethyl acrylate-co-dimethylaminoethyl methacrylate), poly (hydroxypropyl acrylate-co-dimethylaminoethyl methacrylate), poly (hydroxypropyl acrylate-co-methacrylamidopropyltrimethylammonium chloride), poly (acrylamide-co-diallyl dimethylammonium acid amylamide-methacrylamidopropyltrimethyl ammonium chloride-co-acrylic acid),

ii. Polyethyleneimine and its derivatives

They are commercially available under the trade name Lupasol from BASF AG Ludwigschaefen, Germany. In one embodiment, the polyethylene derivative is an amide derivative of polyethyleneimine, which is sold under the trade name Lupoasol SK. Alkoxylated polyethyleneimine is also included; alkylpolyethyleneimine and quaternized polyethyleneimine.

iii. Polyamidoamine-Epichlorohydrin (PAE) Resins

PAE resin is a condensation product of polyalkylene polyamine with polycarboxylic acid. The most common PAE resins are condensation products of diethylenetriamine with adipic acid followed by reaction with epichlorohydrin. They are available from Hercules Inc. of Wilmington DE under the trade name Kymene or from BASF A.G. under the trade name Luresin. Such polymers are described in Wet Strength Resins And Their Applications edited by L.L. Chan, TAPPI Press (1994).

Anionic Surfactant

The anionic surfactant useful for a given detergent for washing is typically the surfactant most commonly used to remove dirt and contaminants during washing and to form bulk and / or elastic foam during normal use. Thus, such an anionic surfactant typically has a foaming profile of at least about 5 cm, or from about 8 cm to 25 cm, as measured by the foam testing protocol below in this application. The level of anionic surfactant is from about 0.5%, 1%, 2%, 5% or 8% to about 20%, 30%, 40%, 50% by weight of the detergent for washing.

In an embodiment, the anionic surfactant comprises an anionic moiety or a plurality of anionic moieties. Not intending to be bound by theory, it is believed that the anionic fragment allows the anionic surfactant to bind a granular composition to control foaming coated with a cationic polymer and form a coacervate. The coacervate is believed to be capable of adhering and precipitating onto the fabric during washing, then selectively degrading when the concentration of the anionic surfactant during the rinsing step decreases compared to the concentration of the washing solution during the washing, thereby releasing the antifoam composition. In the present invention, the level of anionic surfactant in the washing solution during washing is at least about 80 ppm, 140 ppm, 200 ppm, 400 ppm, 600 ppm. d. and the concentration of the anionic surfactant during rinsing is not more than 1/4 of the level of the anionic surfactant during washing, for example, is not more than about 200 ppm, about 150 ppm, approximately 100 ppm, approximately 80 ppm, approximately 50 ppm

In an embodiment, the anionic surfactant has an alkyl chain length of from about 6 carbon atoms (C ₆ ) to about 22 carbon atoms (C ₂₂ ) or from about C ₁₂ to about C ₁₈ . With physical mixing, anionic surfactants form a foam at the air-water interface. Foam indicates to consumers the presence of a surfactant to release contaminants, oils, etc. Non-limiting anionic surfactants in this application include:

a) linear alkylbenzenesulfonates (LAS), or C ₁₁ -C ₁₈ LAS;

b) primary branched and random alkyl sulfates (AS), or C ₁₀ -C ₂₀ AS;

c) secondary (2, 3) alkyl sulfates having the formulas (I) and (II), or C ₁₀ -C ₁₈ secondary alkyl sulfates:

или

,

or

,

M in formulas (I) and (II) is hydrogen or a cation providing neutral charge, for example sodium, potassium and / or ammonium. Above x is from about 7 to about 19, or from about 9 to about 15; and y is from about 8 to about 18, or from about 9 to about 14;

d) alkyl alkoxysulfates and alkyl ethoxysulfates (AE _x S), or C ₁₀ -C ₁₈ AE _X S, where x is from about 1 to about 30, or from about 2 to about 10;

e) alkyl alkoxycarboxylates or C ₆ -C ₁₈ alkyl alkoxycarboxylates or with about 1-5 ethoxy (EO) units;

f) mid-chain branched alkyl sulfates, as discussed in US Pat. No. 6,020,303, Cripe, et al., issued February 1, 2000; and U.S. Patent No. 6,060,443, Cripe, et al., issued May 9, 2000;

g) mid-chain branched alkyl alkoxysulfates, as discussed in US Pat. No. 6,008,181, Cripe, et al., issued December 28, 1999; and U.S. Patent No. 6,020,303, Cripe, et al., issued February 1, 2000;

h) modified alkyl benzene sulfonate (MLAS), as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549 and WO 00/23548 .;

h) methyl ether sulfonate (MES); and

i) primary branched or random alkyl or alkenylcarboxylates or containing from about 6 to about 18 carbon atoms.

In an embodiment, the laundry detergent may contain a mixture of anionic surfactants. The anionic surfactant may be a water-soluble salt, or an alkali metal salt, or a salt of sodium and / or potassium.

Foam enhancing co-surfactants can also be used to increase foam during washing. Many such foaming enhancing co-surfactants are often also anionic surfactants and are included in the general anionic surfactant above.

Additional Detergent Ingredients

The balance of detergents for washing usually contains from about 5% to about 70% or from about 10% to about 60% of additional ingredients such as polymer, filler, bleach, chelating agent, calcium carbonate crystal growth inhibitor, perfume, aesthetics, blueing agent, brightener, non-anionic surfactant, and combinations thereof.

Polymer: Suitable polymers include carboxylate polymers, polyethylene glycol polymers, polyester polymers to release contaminants such as terephthalate polymers, amine polymers, cellulose polymers, dye transfer inhibiting polymers, polymer dye blockers such as condensation oligomer obtained by condensation by condensation and epichlorohydrin, optionally in a 1: 4: 1 ratio, hexamethylenediamine derivatives of the polymers and any combination thereof.

Carboxylate polymer: Suitable carboxylate polymers include maleate / acrylate random copolymer or polyacrylate homopolymer. The carboxylate polymer may be a polyacrylate homopolymer having a molecular weight of from 4000 Da to 9000 Da or from 6000 Da to 9000 Da. Other suitable carboxylate polymers are copolymers of maleic acid and acrylic acid and may have a molecular weight in the range of 4000 Da to 90,000 Da.

Polyethylene glycol polymer: Suitable polyethylene glycol polymers include randomized grafted copolymers comprising: (i) a hydrophilic framework containing polyethylene glycol, and (ii) a hydrophobic side chain (s) selected from the group consisting of: C4-C25 alkyl group, polypropylene, polybutylene saturated vinyl ester of C1-C6 monocarboxylic acid, C1-C6 alkyl ester of acrylic or methacrylic acid, and mixtures thereof. Suitable polyethylene glycol polymers have a polyethylene glycol backbone with randomly grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol skeleton may be in the range from 2000 Da to 20,000 Da or from 4000 Da to 8000 Da. The ratio of the molecular weight of the polyethylene glycol framework and the polyvinyl acetate side chains may be in the range from 1: 1 to 1: 5 or from 1: 1.2 to 1: 2. The average number of grafting sites for ethylene oxide units may be less than 1 or less than 0.8, the average number of grafting sites for ethylene oxide units may be in the range of 0.5 to 0.9, or the average number of grafting sites for ethylene oxide units may be a range from 0.1 to 0.5 or from 0.2 to 0.4. A suitable polyethylene glycol polymer is available under the name Sokalan HP22 from BASF.

Polyester Polymers for Release of Pollution: Suitable polyester polymers for release of pollution have a structure as defined by one of the following structures (I), (II) or (III):

,

,

Where:

a, b and c are from 1 to 200;

d, e and f are from 1 to 50;

Ar is 1,4-substituted phenylene;

sAr is 1,3-substituted phenylene substituted at position 5 with SO ₃ Me;

Me is Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri- or tetraalkylammonium, where the alkyl groups are C1-C18 alkyl, or C2-C10 hydroxyalkyl, or any mixture;

R1, R2, R3, R4, R5 and R6 are independently selected from H or C1-C18 n- or isoalkyl; and

R7 represents a linear or branched C1-C18 alkyl or linear or branched C2-C30 alkenyl or cycloalkyl group with 5 to 9 carbon atoms, or a C8-C30 aryl group, or a C6-C30 arylalkyl group. Suitable polyester polymers for releasing contaminants are terephthalate polymers having the structure of formula (I) or (II) above.

Suitable polyester polymers for the release of contaminants include the Repel-o-tex series of polymers, for example Repel-o-tex SF2 from Rhodia and / or the Techsage series of polymers, for example Texcare SRA300 from Clariant.

Amine polymer: Suitable amine polymers include polyethyleneimine polymers, for example alkoxylated polyalkyleneimines, optionally containing a polyethylene and / or polypropylene oxide block.

Cellulosic polymer: The composition may contain cellulosic polymers, for example, polymers selected from alkylcellulose, alkylalkoxyalkylcellulose, carboxyalkylcellulose, alkylcarboxyalkyl, and any combination thereof. Suitable cellulosic polymers are selected from carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose and mixtures thereof. Carboxymethyl cellulose may have a carboxymethyl substitution degree of from 0.5 to 0.9 and a molecular weight of from 100,000 Da to 300,000 Da. Another suitable cellulosic polymer is a hydrophobically modified carboxymethyl cellulose, for example Finnfix SH-1 from CP Kelco.

Other suitable cellulosic polymers may have a degree of substitution (DS) of 0.01 to 0.99 and a degree of blocking (DB) such that any of DS + DB is at least 1.00 or DB + 2DS-DS2 is at least 1.20. The substituted cellulosic polymer may have a degree of substitution (DS) of at least 0.55. The substituted cellulosic polymer may have a degree of blockage (DB) of at least 0.35. The substituted cellulosic polymer may have a DS + DB of 1.05 to 2.00. A suitable substituted cellulosic polymer is carboxymethyl cellulose.

Another suitable cellulosic polymer is cationically modified hydroxyethyl cellulose.

Dye Transfer Inhibition Polymer: Suitable dye transfer inhibition polymers (DTI) include polyvinylpyrrolidone (PVP), vinyl copolymers of pyrrolidone and imidazoline (PVPVI), polyvinyl N-oxide (PVNO), and any mixture thereof.

Hexamethylene diamine derivatives of the polymer: Suitable polymers include hexamethylene diamine derivatives of the polymer, typically having the formula:

R ₂ (CH ₃ ) N + (CH ₂ ) ₆ N + (CH ₃ ) R _{2 ·} 2X-,

where X- is an acceptable counterion, for example chloride, and R is a poly (ethylene glycol) chain with an average degree of ethoxylation from 20 to 30. Optionally, the poly (ethylene glycol) chains may independently have terminal sulfate and / or sulfonate groups, typically with a charge , balancing by reducing the number of X-counterions, or (in the case of an average degree of sulfation per molecule of more than two) the introduction of Y + counterions, for example sodium cations.

Filler: Detergent for washing can contain up to 60% of the filler. Suitable excipients include sulfate salts and / or bio-filler materials.

Sulfate salt: A suitable sulfate salt is sodium sulfate. The sulfate salt may have a weighted average particle size of 100 to 500 micrometers, alternatively, the sulfate salt may have a weighted average particle size of 10 to 25 micrometers.

Bio-filler material: Acceptable bio-filler material is alkali-treated agricultural waste.

Bleach: The composition may contain bleach. Alternatively, the composition may be substantially free of bleach; essentially being free means "not specifically added." Suitable bleach includes bleach activators, sources of available oxygen, preformed peracids, bleach catalysts, reducing bleach, and any combination thereof. If present, the bleach, or any component thereof, for example a preformed peracid, may be coated, for example encapsulated, or bound to clathrochelate, for example, urea or cyclodextrin.

Whitening Activator: Suitable whitening activators include: tetraacetylethylenediamine (TAED); oxybenzenesulfonates such as nonanoyloxybenzenesulfonate (NOBS), caprylamidononoyloxybenzenesulfonate (NACA-OBS), 3,5,5-trimethylhexanoyloxybenzenesulfonate (Iso-NOBS), dodecyloxybenzenesulfonate and any mixture thereof (LOBS); caprolactams; pentaacetate glucose (PAG); quaternary ammonium nitrile; imide whitening activators such as N-nonanoyl-N-methyl-acetamide; and any mixture thereof.

Source of available oxygen: A suitable source of available oxygen (AvOx) is a source of hydrogen peroxide, such as percarbonate salts and / or perborate salts, such as sodium percarbonate. The peroxide source may be at least partially coated or even completely coated with a coating ingredient, such as a carbonate salt, sulfate salt, silicate salt, borosilicate, or any mixture thereof, including mixed salts. Suitable percarbonate salts may be prepared by a fluidized bed method or crystallization process. Suitable perborate salts include sodium perborate monohydrate (PB1), sodium perborate tetrahydrate (PB4) and anhydrous sodium perborate, which is also known as effervescent sodium perborate. Other suitable sources of AvOx include persulfate, such as oxone. Another acceptable source of AvOx is hydrogen peroxide.

Preformed Perxylota: An acceptable preformed Perxylota is N, N-phthaloylamino peroxycaproic acid (PAP).

Bleaching catalyst: Suitable bleaching catalysts include oxaziridinium based bleaching catalysts, transition metal based bleaching catalysts and bleaching enzymes.

Oxaziridinium-based whitening catalyst: An acceptable oxaziridinium-based whitening catalyst has the formula:

,

,

where: R1 is selected from the group consisting of: H, a branched alkyl group containing from 3 to 24 carbon atoms, and a linear alkyl group containing from 1 to 24 carbon atoms; R1 may be a branched alkyl group containing from 6 to 18 carbon atoms, or a linear alkyl group containing from 5 to 18 carbon atoms, R1 may be selected from the group consisting of: 2-propylheptyl, 2-butyl octyl, 2-pentylnonyl, 2-hexyl decyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso-decyl, iso-tridecyl and iso-pentadecyl; R2 is independently selected from the group consisting of: H, a branched alkyl group containing from 3 to 12 carbon atoms, and a linear alkyl group containing from 1 to 12 carbon atoms; optionally R2 is independently selected from H and methyl groups; and n is an integer from 0 to 1.

Transition Metal Bleaching Catalyst: The composition may include a transition metal bleaching catalyst, typically containing cations of copper, iron, titanium, ruthenium, tungsten, molybdenum and / or manganese. Suitable transition metal-based bleaching catalysts are manganese-based transition metal bleaching catalysts.

Reducing Bleach: The composition may contain a reducing bleach. However, the composition may be substantially free of reducing bleach; essentially being free means "not specifically added." Suitable reducing bleach includes sodium sulfite and / or thiourea dioxide (TDO).

Auxiliary bleach particle: The composition may comprise an auxiliary bleach particle. Typically, the auxiliary bleach particle contains a whitening activator and a peroxide source. The presence of a large amount of a bleaching activator relative to the source of hydrogen peroxide in the auxiliary bleach particle may be particularly suitable. The mass ratio of the bleaching activator and the source of hydrogen peroxide present in the particle auxiliary bleach may be at least 0.5: 1, at least 0.6: 1, at least 0.7: 1, 0.8: 1, or at least 0.9: 1, or 1.0: 1.0, or even 1.2: 1, or higher.

The auxiliary bleach particle may comprise: (i) a bleach activator, for example, TAED; and (ii) a source of hydrogen peroxide, for example sodium percarbonate. The whitening activator can, at least partially or even completely, cover the source of hydrogen peroxide.

The auxiliary bleach particle may contain a binder. Suitable binders are cellulosic polymers, for example carboxymethyl cellulose, and surfactants, including anionic detergents, for example linear C11-C13 alkylbenzenesulfonate.

The auxiliary bleach particle may comprise a bleaching catalyst, for example, an oxaziridinium-based whitening catalyst.

Photo bleach: Suitable photo bleaches are zinc and / or aluminum sulfonated phthalocyanines.

Chelating agent: Suitable chelating agents are selected from: diethylenetriamine pentaacetate, diethylenetriamine penta (methylphosphonic acid), ethylenediamine-N'N'-di-succinic acid, ethylenediamine tetraacetate, ethylenediamine tetra (methylenephosphonic acid), hydroxyethane and any combination. A suitable chelating agent is ethylenediamine-N'N'-di-succinic acid (EDDS) and / or hydroxyethane diphosphonic acid (HEDP). The laundry detergent composition may contain ethylenediamine-N'N'-disuccinic acid or a salt thereof. Ethylenediamine-N'N'-di-succinic acid may be in the S, S enantiomeric form. The composition may include a disodium salt of 4,5 dihydroxy-m-benzenedisulfonic acid. Suitable chelating agents can also be calcium crystal growth inhibitors.

Calcium carbonate crystal growth inhibitor: The composition may comprise a calcium carbonate crystal growth inhibitor, for example, selected from the group consisting of: 1-hydroxyethane diphosphonic acid (HEDP) and its salts; N, N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and its salts; 2-phosphonobutane-1,2,4-tricarboxylic acid and its salts; and any combination thereof.

Fragrances: Acceptable fragrances include perfume microcapsules, polymer delivery perfume delivery systems including perfume / Schiff base polymer complexes, starch-encapsulated combinations of fragrance fragrance notes, fragrance-loaded zeolites, floral combinations of fragrance fragrance notes, and any combination thereof. An acceptable perfume microcapsule is melamine formaldehyde-based, typically containing perfume, which is encapsulated in melamine formaldehyde. It may be very suitable for such perfume microcapsules to include cationic material and / or cationic precursor material in a shell, such as formamide polyvinyl (PVF) and / or cationically modified hydroxyethyl cellulose (catHEC).

Aesthetic substances: Acceptable particles of aesthetic substances include soap rings, lamellar particles of aesthetic substances, gelatinous substrates, speckles of carbonate and / or sulfate salts, particles of colored clay and any combination thereof.

Blueing agents are typically a slightly blueing dye and / or pigment that adheres to the tissues and helps to hide yellowish shades and colors on the fabrics so as to make the fabric look more white. Blueing agents suitable for use in this application include: Polar Brilliant Blue GAW 180 percent, sold by Ciba-Geigy S.A., Basel, Switzerland (similar to C.I. [“Color Index”] 61135 - Acid Blue 127); FD&C Blue No. 1 (C.I. 42090), Rhodamine BM (C.I. 45170); Pontacyl Light Yellow 36 (similar to C.I. 18820); Acid yellow 23; Pigmasol blue; Acid blue 3; Polar Brilliant Blue RAW (C.I. 61585 - Acid Blue 80); Phthalocyanine Blue (C.I. 74160); Phthalocyanine Green (C.I. 74260); and Ultramarine Blue (C.I. 77007 - Pigment Blue 29). Further examples of acceptable bluing agents are described in US Pat. No. 3,931,037 issued January 6, 1976 to Hall and US Patent No. 5,605,883 issued February 25, 1997 to Iliff, et al. In an embodiment of this application, the bluing agent is Ultramarine Blue, available from various suppliers around the world.

Clarifiers convert invisible light into visible light, thereby making fabric and clothing brighter, whiter and / or their colors more emphasized. Non-limiting examples of clarifiers useful in this application include clarifier 15, clarifier 49, manufactured by Ciba Geigy, Paramount, Shanghai Yulong and others. Blueing agents and brighteners are typically present at levels from about 0.005% to about 3%.

Other surfactants useful in this application include cationic surfactants, nonionic surfactants, and amphoteric surfactants. Such surfactants are well known for use in laundry detergents and are typically present at levels from about 0.2% or 1% to about 40% or 50%.

Production method

These laundry detergents are prepared by mixing the granular foam control composition with an existing laundry detergent comprising an anionic surfactant. The existing laundry detergent before mixing with the granular foam control composition is typically in the form of water-soluble granules formed by agglomeration and / or spray drying and / or extrusion, and their production process can be a batch or continuous process, both of which are good known in the art.

Foaming control compositions are first prepared by mixing a foaming control agent containing a polysiloxane liquid, a hydrophobic filler, and optionally an organosilicon resin, together with an organic additive. The above mixture in non-aqueous liquid form is precipitated on a particulate water-soluble inorganic carrier. The charged polymer may be deposited on a particulate carrier in combination with a mixture of a foam control agent and an organic additive, or sequentially. If a charged polymer is deposited on a particulate carrier in combination with a mixture of a foaming control agent and an organic additive, it can be pre-mixed with a foaming control agent and an organic additive, or precipitated onto carrier particles simultaneously with a mixture of a foaming control agent and an organic additive. The cationic polymer (D) is generally precipitated in liquid form, for example, from an aqueous solution or dispersion.

The mixture of the foam control agent and the organic additive is preferably deposited on carrier particles at a temperature at which the organic additive is liquid, for example at a temperature in the range of about 45-100 ° C. As the mixture cools on carrier particles, it hardens to a structure that enhances the effectiveness of the composition for controlling foaming. The foam control composition is preferably prepared by an agglomeration process in which a foam control composition containing a foam control agent and an organic additive is sprayed onto carrier particles while the particles are mixed. In one embodiment, the particles are mixed in a high shear mixer through which the particles pass continuously.

One type of suitable mixer is a high shear vertical continuous mixer in which a foam control composition is sprayed onto particles. One example of such a mixer is available under the name Flexomix mixer from Hosokawa Schugi.

Alternative suitable mixers that may be used include high shear horizontal mixers in which an annular layer of powder-liquid mixture is formed in the mixing chamber, with a residence time of from a few seconds to about 2 minutes. Examples of this family of machines are axial mixers, for example TAG series from LB, RM-type machines from Rubberg-Mischtechnik or other axial mixers supplied by Lodige, and paddle mixers, for example, CB series from Lodige, Corimix from Drais-Manheim and Conax from Ruberg Mischtechnik.

Other possible mixers that can be used in the process of the present invention are Glatt granulators, ploughshare mixers, which, for example, are sold from Lodige GmbH, double opposed rotary vane mixers, commercially available under the name Forberg, intensive mixers, including a lever for intensively mixing the layers in a rotating cylindrical vessel, commercially available under the name Tour R from Eirich, under the name Zig-Zag from Patterson-Kelley and under the name HEC from Niro.

The index of foaming during washing and the index of foaming during rinsing

The washing foam index is used to compare the amount of foam formed during the washing step with a given washing detergent containing a granular foam control composition as compared to the washing detergent itself without this granular foam control composition as a control. In this application, the volume of the foam is measured by the height of the foam after the standardized washing process described below.

The rinsing foaming index is used to compare the amount of foam remaining after rinsing this detergent containing a granular composition for controlling foaming compared to detergents for washing on their own as a control. In this application, the volume of the foam is measured by the surface area of the foam in the rinse sink after the standardized rinse process described below.

This washing detergent, which is used for experiments, contains, by weight of the detergent for washing, 0.05% of this and a comparative granular composition for controlling foaming, 11% linear alkylbenzenesulfonate, 1% alkyl dimethylhydroxyethylammonium chloride, 3.5% C14- 15 alkyl ethoxylated alcohols having a molar average degree of ethoxylation of 9, 20% sodium aluminosilicate (Zeolite), 15% sodium carbonate, 28% sodium sulfate, 2% sodium silicate, 1.5% carboxymethyl cellulose, 4% polyacrylic acid, 2% percarbox sodium nata, 0.5% tetraacetylethylenediamine (TAED) and comprises enzymes, etc., that is the total of all components to 100%.

Standard washing process

1) Fill the sink with 2 L of deionized water (4 g per gallon) and dissolve the laundry detergents to a concentration of 3500 ppm. in water and mix by rotation for 2 minutes until completely dissolved and a washing solution is formed.

2) Place a piece of cloth in the washing solution and soak for 5 minutes.

3) For each piece of fabric, rub it 5 times, immersing it again in the washing solution between the friction.

4) Carefully wring out the scrubbed cloth without touching the resulting foam.

5) Measure the total height of the foam and washing solution by taking the average of five measurements, including one center point and four edge points of the sink.

6) Measure the height of the washing solution in the sink by removing foam from the sink.

7) Get the height of the foam by subtracting the measurement obtained in step 6) from the measurement obtained in step 5).

Standard rinse process

1) Place the washed and squeezed piece of fabric in a new sink containing 2 L of fresh deionized water (4 g per gallon) by controlling the transfer of the washing solution as 200 ± 5 g (transfer = total weight after washing - dry fabric weight). Rinse each piece of fabric with 3 careful rubbing.

2) Take a photograph of the foam coating on the surface of the wash water for 5-10 seconds after removing a piece of cloth from the water.

As a summary, the conditions set for washing and rinsing are presented in the table below.

Product concentration 3500 ppm Soaking time 5 minutes Water volume 2 l Friction during washing 5 friction Hardness of water 4 g per gallon, Ca: Mg = 4: 1 1st / 2nd rinse time 3 friction Water temperature 20-25 ° C Rinse method Handwash Assessment Method A ruler for measuring the height of the foam with a coating area = 100% or a photograph for the percentage of coverage if coverage is <100% the cloth 1 piece of terry towel (20 cm × 20 cm), 2 pieces of knitted cotton fabric (40 cm × 40 cm). Total dry weight = 115 ± 3 g

EXAMPLES

The following examples further describe and demonstrate embodiments that are within the scope of the present invention. The examples are given for illustrative purposes only and should not be construed as limitations of the present invention, since many of their variations are possible without departing from the essence and scope of the present invention.

The following Examples 1-9 describe the preparation of granular foam control compositions in accordance with the present invention, while Comparative Examples C1-C3 are not included in the scope of the present invention. Granular foam control compositions are prepared by mixing a foam control agent, an organic additive composition, a particulate water-soluble inorganic carrier and a charged polymer together. If such granular foam control compositions are obtained, each of them is then mixed with an existing laundry detergent to form a given laundry detergent. As described in the previous paragraph, this detergent for washing, which is used for experiments, contains, by weight, detergent for washing, 0.05% of this and a comparative granular composition for controlling foaming, 11% of linear alkyl benzene sulfonate, 1% alkyl dimethylhydroxyethylammonium chloride, 3 5% C14-15 of an alkyl ethoxylated alcohol having a molar average degree of ethoxylation of 9, 20% sodium aluminosilicate (Zeolite), 15% sodium carbonate, 28% sodium sulfate, 2% sodium silicate, 1.5% carboxymethyl cellulose, 4% polyacrylic acid, 2% sodium percarbonate, 0.5% tetraacetylethylenediamine (TAED) and contains enzymes, etc., which makes the total amount of all components up to 100%.

Example 1

Six percent (6%) by weight of the treated precipitated silica, available under the name Evonik Sipernat D10, and 1% partially hydrophobic silica, available under the Evonik name R972, was dispersed in 86.3% polydiorganosiloxane liquid with a polymerization degree of 65 and containing 80 mol .% methyl ethyl siloxane groups, 19 mol% methyl 2-phenylpropyl (obtained from α-methyl styrene) siloxane groups and 1 mol% divinyl cross-linking groups. 6.7% by weight of 60% by weight of a solution of an organosiloxane resin containing trimethyl siloxane units and SiO ₂ units in an M / Q ratio of 0.65 / 1 in octyl stearate (70% solids) was added. The mixture was homogenized using a high shear mixer to form an FC1 foam control agent.

Fourteen (14) parts of the above FC1 foaming control agent were mechanically mixed with 9 parts of glyceryl tribeneate from Oleon. FC1 and molten glyceryl tribeneate were mixed at 70 ° C. Glyceryl monobegenate and polydiorganosiloxane liquid are miscible and the mixture has a melting point of 65 ° C. A mixture of glyceryl tribegenate and FC1 and 4.5 parts of a 1% aqueous solution of Polyquaternium-10 JR 30M cationic polymer was slowly poured into a mixer, where 73.5 parts of sodium sulfate powder was already mixed. Polyquaternium-10 JR 30M is provided by Dow Chemicals and is a quaternary ammonium polymer salt formed by the reaction of hydroxyethyl cellulose with trimethyl ammonium substituted by epoxide and has a Mw of 800,000 and a charge density of 1.25 meq / g. The mixture was continuously stirred to obtain granular material in the form of particles. The water contained in this granular foam control composition was removed in a fluidized bed using air at 30 ° C.

A granular composition for controlling foaming was obtained.

Example 2

Another similar FC2 foam control agent was obtained, substantially the same as FC1, except that the polydiorganosiloxane liquid was different from the liquid in FC1. Instead, FC2 used 86.3% polydiorganosiloxane liquid, which has a degree of polymerization of 65 and contains 80 mol% of methyl dodecyl siloxane groups, 20 mol% of methyl 2-phenylpropyl (derived from [alpha] methyl styrene) siloxane groups.

Thirteen and a half (13.5) parts of the above FC2 Foam Control Agent was mechanically mixed with 9 parts of Oleon Glyceryl Tristearate. FC2 and molten glyceryl tristearate were mixed at 70 ° C. Glyceryl tristearate and polydiorganosiloxane liquid are miscible and the mixture has a melting point of 62 ° C. A mixture of glyceryl tristearate and FC2 and 4 parts of a 1% aqueous solution of Polyquaternium-10 JR 30M cationic polymer was slowly poured into a mixer, where 73 parts of sodium sulfate powder were already mixed. The mixture was continuously stirred to obtain granular material in the form of particles. The water contained in this granular foam control composition was removed in a fluidized bed using air at 30 ° C.

A granular composition for controlling foaming was obtained.

Example 3

Twelve and a half (12.5) parts of the above FC2 foam control agent were mechanically mixed with 7.5 parts of glyceryl tribeneate from Oleon. FC2 and molten glyceryl tristearate were mixed at 70 ° C. Glyceryl tribegenate and polydiorganosiloxane liquid are miscible, and the mixture had a melting point of 65 ° C. A mixture of glyceryl tribegenate and FC2, and 5 parts of a 6.2% aqueous solution of the RAM / MARTSAS copolymer having a molecular weight of 1,100,000 Da from Nalco containing 88 parts of polyacrylamide monomer units (RAM) and 12 parts of methacrylamide propyl trimethylammonium chloride monomer units, slowly discharged (MAP) a mixer where 75 parts of sodium sulfate powder was already mixed. The mixture was continuously stirred to obtain granular material in the form of particles. The water contained in this granular foam control composition was removed in a fluidized bed using air at 30 ° C.

A granular composition for controlling foaming was obtained.

Examples 4-6

Thirteen and a half (13.5) parts by weight of the FC2 foam control agent was mixed with 9 parts of molten glyceryl tribeneate at 70 ° C. A mixture of glyceryl tribegenate and FC2 and 4.5 parts of a 1% aqueous solution of a cationic polymer was slowly poured into a mixer, where 73.5 parts of sodium sulfate powder was already mixed. The mixture was continuously stirred to obtain granular material in the form of particles. The water contained in this granular foam control composition was removed in a fluidized bed using air at 30 ° C. Got granular compositions for controlling foaming.

The cationic polymers used in Examples 4-6 are:

Example 4 - Polyquaternium-10 / JR 30M.

Example 5 - Polyquaternium-10 / LR 30M, which is a quaternary ammonium polymer salt formed by the reaction of hydroxyethyl cellulose with trimethyl ammonium substituted epoxide, and has a molecular weight of approximately 350,000 and a charge density of 0.7 meq / g.

Example 6 - Polyquaternium-10 / JR 125, which is a quaternary ammonium polymer salt formed by the reaction of hydroxyethyl cellulose with trimethyl ammonium substituted epoxide, and has a molecular weight of 80,000 and a charge density of 1.25 meq / g.

Comparative Example C1

Sixty-nine (69) parts of a zeolite commercially available under the name Ineos Zeolite A were mixed with about 8.5 parts of Croda glyceryl monobegenate, about 13 parts of FC2, and about 9.5 parts of Polyquaternium-10 solution at 1%. The mixture was obtained by mechanical mixing of silicone with molten glyceryl monobegenate at 80 ° C. This mixture and Polyquaternium-10 aqueous solution at 1% were slowly poured into a mixer where zeolite was already present. The mixture was continuously stirred to obtain particulate material. The water contained in the granular material was removed in a fluidized bed using air at 30 ° C.

Comparative Example C2

Sixty-eight (68) parts of sodium sulfate were mixed with about 8 parts of glyceryl monobegenate from Croda, about 12.5 parts of FC2, and about 10.5 parts of an acyl / maleic copolymer from BASF called Sokalan® CP5. The mixture was obtained by mechanical mixing of silicone with molten glyceryl monobegenate at 80 ° C. This mixture and the acrylic / maleic copolymer were slowly poured into a mixer where Na sulfate was already present. The mixture was continuously stirred to obtain particulate material. The water contained in the granular material was removed in a fluidized bed using air at 30 ° C.

Comparative Example C3

Sixty-nine and a half (69.5) parts of sodium sulfate were mixed with about 9.5 parts of microcrystalline wax from A&E Connock, about 14 parts of FC2 and about 6.5 parts of a polyMADAME aqueous solution at 1%, which is polydimethylaminoethyl methacrylate without charge density, from Dow Corning. The mixture was obtained by mechanically mixing silicone with molten microcrystalline wax, this mixture and polyMADAME aqueous solution at 1% were slowly poured into a mixer where sodium sulfate was already present. The mixture was continuously stirred to obtain particulate material. The water contained in the granular material was removed in a fluidized bed using air at 30 ° C.

Comparative Example C4

Eighty (80) parts of sodium sulfate were mixed with about 11 parts of glyceryl tribenegen from Oleon and about 9 parts of Polyquaternium-10 JR 30M solution at 0.5%. The molten glyceryl tribegenate and Polyquaternium-10 JR 30M aqueous solution at 0.5% were slowly poured into a mixer where sodium sulfate was already present. The mixture was continuously stirred to obtain particulate material. The water contained in the granular material was removed in a fluidized bed using air at 30 ° C.

Detergent for washing containing the granular antifoam compositions described in Examples 1-6 and comparative examples C1-C4 was tested for a foaming index during washing and during rinsing in accordance with the testing protocol described in this application above. The results are shown in Table 1 below.

Table 1 Examples one 2 3 four 5 6 C1 C2 C3 C4 Washing Foam Index 67% 78% 96% 83% 79% 66% one hundred% 59% 67% 89% Rinse Foam Index 40% fifteen% twenty% fifty% fifty% 25% one hundred% 80% 60% 95% MW cationic polymer 800,000 80,000 0 800,000 800,000 300000-400000 80,000 Insoluble Particle Carrier Anionic polymer Uncharged polymer + other wax No silicone fluid Charge density (meq / g) 1.25 1.25 1.25 1.25 0.7 1.25 Cationicity (meq * Yes / g) 1000 1000 1000 1000 210-280 one hundred

You can see that Examples 1-6, using this detergent for washing, containing granular compositions for controlling foaming, all have a minimal effect on the foam during washing (index of foaming during washing more than 65%, i.e. less than 35% reduce foam during washing), and have a significantly reduced amount of foam during rinsing (foaming index when rinsing less than 50%).

Comparative Example C1, using a carrier based on insoluble particles in the formation of the granular composition to control foaming, had no effect on the rinsing foam (foaming index when rinsing more than 50%), comparative example C2, using an anionic polymer for the granular composition to control foaming, had a significant effect on the foam during washing (its foaming index is less than 65%), and does not reduce the amount of foam when rinsing, fact cally foam rinse more than in the wash. Comparative Example C3, using a different cationic polymer and a different wax than the present invention, demonstrates acceptable washing foam, but reducing the foam when rinsing is not sufficient (foam when rinsing more than 50%). Comparative example C4 without silicone for a granular composition for controlling foaming shows only a decrease in foam when rinsing (index foaming when rinsing 95%).

Example 7

Fourteen (14) parts by weight of an FC2 foam control agent were mechanically mixed with 9 parts of glyceryl monobegenate from Croda. FC2 and molten glyceryl monobegenate were mixed at 70 ° C. Glyceryl monobegenate and polydiorganosiloxane liquid are miscible and the mixture has a melting point of 69 ° C. A mixture of glyceryl monobegenate and FC2 and 3 parts of a 1% aqueous solution of Polyquaternium-10 / JR 30M cationic polymer was slowly poured into a mixer, where 78 parts of sodium sulfate powder were already mixed. The mixture was continuously stirred to obtain granular material in the form of particles. The water contained in this granular foam control composition was removed in a fluidized bed using air at 30 ° C. A granular composition for controlling foaming was obtained.

Example 8

Eight (8) parts by weight of an FC2 foam control agent were mechanically mixed with 5 parts of Oleon glyceryl tristearate. FC2 and molten glyceryl tristearate were mixed at 80 ° C. A mixture of glyceryl tristearate and FC2 and 6.5 parts of a 6.2% aqueous solution of cationic polymer CP1 were slowly poured into a mixer, where 73 parts of sodium sulfate powder were already mixed. The mixture was continuously stirred to obtain granular material in the form of particles. The water contained in this granular foam control composition was removed in a fluidized bed using air at 30 ° C. A granular composition for controlling foaming was obtained.

Example 9

Nine and a half (9.5) parts by weight of the FC2 foam control agent were mechanically mixed with 6.5 parts of glyceryl tristearate from Sasol. FC2 and molten glyceryl tristearate were mixed at 80 ° C. Glyceryl tristearate and polydiorganosiloxane liquid are miscible and the mixture has a melting point of 70 ° C. A mixture of glyceryl tristearate and FC2 and 4 parts of a 6.2% aqueous solution of cationic polymer CP1 was slowly poured into a mixer, where 80 parts of sodium sulfate powder were heated at 70 ° C and already mixed. The mixture was continuously stirred to obtain granular material in the form of particles. The water contained in this granular foam control composition was removed in a fluidized bed using air at 30 ° C. A granular composition for controlling foaming was obtained.

Laundry detergent containing the granular anti-foaming composition described in Examples 7-9 was tested for foaming during washing and rinsing according to the testing protocol described above, except that 3 pieces of knitted cotton that had a total dry weight of 120 ± 5 g used instead of 1 towel and 2 pieces of knitted cotton, which had a total dry weight of 115 ± 3 g, used in Examples 1-6. The height of the foam when washing in the washing sink and the coating of foam when rinsing in the rinse sink are presented in table 2 below in comparison with the height of the foam in the same washing sink and the coating of foam in the same rinse, formed only with detergent without granular foaming composition as a control.

table 2 The height of the foam in the sink when washing The surface of the foam in the sink when rinsing Control: detergent only 6.9 cm one hundred% Example 7 6.7 cm 10% Example 8 6.4 cm fifteen% Example 9 6.5 cm twenty%

The dimensions and values described in this application should not be construed as strictly limited to the exact numerical values that are indicated. Instead, unless otherwise indicated, each such dimension is intended to mean both the cited value and a functionally equivalent range covering the given value. For example, a dimension described as “40 mm” is intended to mean “approximately 40 mm”.

Each document cited in this application, including any patents or applications cited as cross-references, or related patents or applications, is hereby fully incorporated into this application by reference, unless otherwise expressly excluded or otherwise limited. The citation of any document is not an assumption that it represents the prior art with respect to any invention described or claimed in this application, or that it, taken individually or in any combination with any other reference or references, leads a doctrine, suggests or describes any such invention. Additionally, to the extent that the meaning or definition of a term in this written document is contrary to any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to the term in this written document will be defining.

While specific implementations in accordance with the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the present invention. Therefore, the claims of the present invention, which are provided, are intended to cover all such changes and modifications that are within the scope of the present invention.

Claims (12)

1. A detergent for washing containing a granular composition for controlling foaming and an anionic surfactant, wherein said granular composition for controlling foaming contains:
(a) a foam control agent comprising:
i. polydiorganosiloxane liquid containing units of the formula

where each R group, which may be the same or different, is selected from an alkyl group containing from 1 to 36 carbon atoms, or an aryl group or an aralkyl group containing from 1 to 36 carbon atoms, wherein the average number of carbon atoms in R groups is, at least 1.3;
ii. hydrophobic filler dispersed in a polydiorganosiloxane liquid;
iii. an organosilicon resin, which is a siloxane resin, consisting of monovalent trihydrocarboxyloxy (M) groups of the formula R ″ ₃ SiO _1/2 and tetrafunctional Q groups SiO _4/2 , where R ″ means an alkyl group and the quantitative ratio of Μ and Q groups is in the range from 0.4: 1 to 1.1: 1;
(b) an organic additive composition comprising a polyol ester, which is a glycerol ester with a carboxylic acid containing from 7 to 36 carbon atoms, and which is miscible with said polydiorganosiloxane liquid, wherein the mixture of the organic additive and polydiorganosiloxane liquid has a melting point of approximately 45 ° C to approximately 100 ° C;
(c) a water-soluble inorganic particulate carrier;
(d) a charged polymer selected from quaternary ammonium polymer salts and copolymers thereof with a total charge density of from about 0.05 to about 23 meq / g and a molecular weight of from about 80,000 to about 4,000,000 daltons, said charged polymer having a cationicity parameter ( molecular weight of the product · charge density / 1000) more than 50 meq · Yes / g. 2. Detergent for washing according to claim 1, characterized in that said polydiorganosiloxane liquid is a polysiloxane containing at least 10% diorganosiloxane units of the formula

and up to 90% of diorganosiloxane units of the formula

where X is a divalent aliphatic organic group bonded to silicon via a carbon atom; Ph is an aromatic group; Υ means an alkyl group containing from 1 to 4 carbon atoms; and Y ′ means an aliphatic hydrocarbon group containing from 1 to 24 carbon atoms. 3. The detergent for washing according to claim 1, characterized in that the polydiorganosiloxane liquid is a polysiloxane containing 50-100% diorganosiloxane units of the formula

where Υ means an alkyl group containing from 1 to 4 carbon atoms, and Ζ means an alkyl group containing from 6 to 18 carbon atoms. 4. Detergent for washing according to claim 3, characterized in that the polydiorganosiloxane liquid further comprises up to 50% of diorganosiloxane units of the formula

where Υ means an alkyl group containing from 1 to 4 carbon atoms. 5. Detergent for washing according to any one of paragraphs. 1-4, characterized in that the polyol as one ester is a glycerol triester, essentially completely esterified with carboxylate groups, each of which contains from 14 to 22 carbon atoms. 6. Detergent for washing according to any one of paragraphs. 1-4, characterized in that the polyol as one ester is a monocarboxylate or polycarboxylate, in which each carboxylate group contains from 18 to 22 carbon atoms. 7. Detergent for washing according to any one of paragraphs. 1-4, characterized in that the water-soluble inorganic carrier in the form of particles selected from the group consisting of sodium sulfate, sodium carbonate, sodium bicarbonate, and combinations thereof. 8. Detergent for washing according to any one of paragraphs. 1-4, characterized in that the charged polymer is a cationic polysaccharide. 9. Detergent for washing according to any one of paragraphs. 1-4, characterized in that the charged polymer is a synthetic additive polymer of General structure

where each R ¹ independently represents hydrogen, C ₁ -C ₁₂ alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, -OR _a or -C (O) OR _a , where R _{a is} selected from hydrogen and C ₁ -C ₂₄ alkyl and mixtures thereof; each R ² independently represents hydrogen, hydroxyl, halogen, C ₁ -C ₁₂ alkyl, -OR _a , substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocycle or heterocycle; and each Ζ independently represents hydrogen, halogen; linear or branched C ₁ -C ₃₀ alkyl, nitrile, N (R ₃ ) ₂ -C (O) N (R ₃ ) ₂ ; -NHCHO (formamide); -OR ³ , -O (CH ₂ ) _n N (R ³ ) ₂ , -O (CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , -C (O) OR ⁴ ; -C (O) N- (R ³ ) ₂ , -C (O) O (CH ₂ ) _n N (R ³ ) ₂ , -C (O) O (CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , -OCO (CH ₂ ) _n N (R ³ ) ₂ , -OCO (CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , -C (O) NH- (CH ₂ ) _n N (R ³ ) ₂ , -C (O) NH (CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , - (CH ₂ ) _n N (R ³ ) ₂ , - (CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- or non-aromatic nitrogen heterocycle comprising a quaternary ammonium ion, a heterocycle containing N-oxide moiety, an aromatic nitrogen containing heterocycle wherein one or more quaternized nitrogen atoms; aromatic nitrogen-containing heterocycle, where at least one nitrogen atom is an N-oxide; each R ₃ independently represents hydrogen, C ₁ -C ₂₄ alkyl, C ₂ -C ₈ hydroxyalkyl, benzyl or substituted benzyl; each R ₄ independently represents hydrogen or C ₁ -C ₂₄ alkyl or - (CH ₂ -CHR ₅ -O) _m -R ³ where R ₅ independently represents hydrogen or C ₁ -C ₆ alkyl; X is a water soluble anion; and n is from 1 to 6; with the proviso that at least one group Ζ per molecule is selected from —O (CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , —C (O) OR ⁴ ; -C (O) N- (R ³ ) ₂ , -C (O) O (CH ₂ ) _n N (R ³ ) ₂ , -C (O) O (CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , -OCO (CH ₂ ) _n N (R ³ ) ₂ , -OCO (CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , -C (O) NH- (CH ₂ ) _n N (R ³ ) ₂ , -C (O) NH (CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , - (CH ₂ ) _n N (R ³ ) ₂ , - (CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- or non-aromatic nitrogen-containing heterocycle containing a quaternary ammonium ion, a heterocyclic ring containing the N-oxide moiety, an aromatic nitrogen containing heterocycle wherein one or more quaternized nitrogen atoms; aromatic nitrogen-containing heterocycle, where at least one nitrogen atom is an N-oxide. 10. A method for cleaning tissue, wherein said method comprises the steps of:
a) provide a detergent for washing according to any one of paragraphs. 1-9;
b) forming a washing solution by diluting said washing detergent, wherein the level of the anionic surfactant of the washing solution is at least 80 ppm;
c) wash the fabric in the washing solution;
d) rinse the tissue in water, while the level of anionic surfactant does not exceed 1/4 of the level in stage b). 11. A method of saving water when washing a fabric, the method comprising the step of washing the fabric according to the method of claim 10, wherein step d) is performed once. 12. A method of saving time when washing the fabric, wherein said method comprises a step of washing the fabric in accordance with the method of claim 10, wherein step d) is performed once.