CN115279877A - Low foaming solid cleaning compositions - Google Patents

Abstract

The present invention is in the field of solid cleaning compositions which have good cleaning properties in the main wash but significantly reduced suds during the rinse. It is an object of the present invention to provide an overall foam reduction during the first rinse. It has been found that by including a specific anionic surfactant, C₈To C₁₈A solid cleaning composition of a water-soluble alkyl carboxylate of a fatty acid and a nonionic surfactant, wherein the solid cleaning composition has a carbonate builder, achieves this in a cleaning process.

Description

Low foaming solid cleaning composition

Technical Field

The present invention relates to a laundry cleaning composition; especially a solid detergent composition with low or no suds in the main wash and which shows a significant reduction in water consumption during rinsing.

Background

Water is becoming an increasingly scarce commodity, particularly in developing countries where people must travel long distances to reach a water source. Thus, there is an increasing need to save water.

One way to save water is to reuse the water and another way to reduce the amount of water used.

Washing processes, including laundry, dishwashing and other household cleaning processes, consume large amounts of water worldwide. These are day-to-day chores in which the use of water and detergents cannot be avoided.

Lather is an important consumer cue and serves as the primary reason consumers perceive that a composition has a cleansing effect. Unfortunately, while good foams are easily produced, they also need to be removed from the substrate after cleaning. Therefore, a balance needs to be struck between producing good foam and thereafter removing the foam.

Laundry formulations such as rinse aids have been used to help reduce foam carried into the rinse water by the laundered fabrics. Rinse aids reduce the amount of water used during the rinse. However, the use of rinse aids adds an extra step and the consumer needs to use additional products in the wash process.

In today's fast-paced world, consumers are looking for a single composition that provides a cleansing effect while reducing water consumption. This need is particularly felt by consumers who live in areas with severe water shortage.

However, it remains a challenge to provide a cleaning composition that produces low or no foam without affecting cleaning performance. The main reason behind this is that conventional cleaning compositions use LAS to provide good stain removal benefits. LAS is an anionic detersive surfactant and is routinely used to achieve the desired cleaning performance, but LAS also generates a large amount of foam when agitated during the washing step. After the washing step, appreciable amounts of surfactant typically remain in the fabric fibers and on the fabric surface. This may be referred to as "residue". As a result, a large amount of foam occurred in the rinsing step. This residue typically persists through multiple rinses, and satisfactory removal of foam, soapy feel, or turbidity in the rinse liquor typically consumes 2 or 3 rinse buckets of clean water.

Accordingly, there is a need for a cleaning composition that reduces, and preferably eliminates, foam without adversely affecting cleaning performance.

Some solutions to this foaming problem during the rinse phase are through the addition of a rinse-initiated defoamer that acts on the foam and suppresses the foam during the rinse phase. However, such rinse-initiated defoamers increase the amount of chemicals incorporated in the composition, and care must be taken to formulate such compositions to avoid release of the defoamer during the cleaning stage. In addition, defoamers are generally expensive and have no other performance benefits to the composition other than foam suppression. It is therefore desirable that their presence be minimized.

Other compositions, such as those disclosed in WO 93/18128 (Unilever), provide a low foaming liquid cleansing composition which exhibits a reduced tendency to form a stable foam. The liquid cleansing composition includes a hydrophobic oil, a first surfactant that forms a sparingly soluble calcium salt in aqueous solution, and a second surfactant that foams and is different from the first surfactant.

Despite previous efforts to provide detergent compositions that are low foaming for laundering fabrics and require a reduced number of rinse steps, there remains a need for solid cleaning compositions that provide good cleaning performance and that generate less or no suds.

It is therefore an object of the present invention to provide a solid cleaning composition which does not foam or generates low foam during the rinsing stage and has excellent cleaning performance.

It is another object of the present invention to provide a solid cleaning composition that requires less than 3 rinses, preferably only one rinse.

It is yet another object of the present invention to provide a solid cleaning composition with improved enzyme stability.

It is another object of the present invention to provide a solid cleaning composition that provides improved stain removal.

It is a further object of the present invention to provide a solid cleaning composition which provides improved bleachable, oily, enzymatic or particulate soil removal.

Summary of The Invention

It has been found that the combination of specific anionic and nonionic surfactants in a carbonate-built solid cleaning composition exhibits good cleaning performance and that the foam generated during the washing step is effectively and completely removed from the washed fabrics in less than 3 rinses, preferably the first rinse.

More specifically, the improved solid cleaning composition includes a specific anionic surfactant, nonionic surfactant, and alkali builder salt, which suppresses the formation of foam in a washing liquid even when a defoaming agent is contained in a small proportion.

It has been found that the solid cleaning compositions of the present invention with specific anionic and nonionic surfactants produce less suds in water of varying hardness than prior detergent compositions. The cleaning compositions of the present invention allow the consumer to use higher levels of detergent and still require less than 3 rinses, preferably a single rinse step, to achieve complete removal of suds, soapy feel and soil from the rinse water. It has been found that aqueous solutions of the cleaning compositions herein produce a very low degree of foaming under conditions of vigorous and/or continuous agitation.

It has been surprisingly found that detergent compositions exhibit stain removal performance at least equivalent to that of a detergent composition comprising LAS entirely.

The terms "fabric," "garment," and "fabric article" as used interchangeably herein are intended to mean any article that is typically cleaned in a conventional laundry process. Thus, the term does not refer specifically to any type of flexible material comprised of a network of natural or synthetic fibers, including natural, synthetic, and synthetic fibers such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, as well as various blends and combinations. It includes clothing, linens, draperies, and fittings. The term also includes other items made in whole or in part of fabric, such as handbags, furniture covers, tarpaulins, and the like.

The term "low sudsing" as used herein means that the foam height or foam volume of the solid cleaning composition according to the present invention is less than that obtained in a comparable composition comprising LAS anionic surfactant. It also includes a reduction in the duration of visible suds during the wash process for cleaning soiled articles compared to compositions containing LAS anionic surfactant.

In a first aspect, there is provided a solid cleaning composition comprising:

i) An anionic non-soap surfactant selected from primary alkyl sulfate surfactants, alkyl ester fatty acid sulfonate surfactants, or mixtures thereof;

ii)C₈to C₁₈Water-soluble alkyl carboxylates of fatty acids;

iii) A nonionic surfactant;

iv) 0 to 0.5 wt% linear alkylbenzene sulphonate surfactant; and

v) a carbonate builder.

These and other aspects, features and advantages of the present invention will become apparent to those of ordinary skill in the art upon review of the following detailed description and the appended claims.

Detailed Description

According to a first aspect of the present invention, a solid cleansing composition is disclosed having an anionic non-soap surfactant selected from a primary alkyl sulfate surfactant, an alkyl ester fatty acid sulfonate or mixtures thereof, C₈To C₁₈Water-soluble alkyl carboxylate salt of fatty acid, nonionic surfactant, 0 to 0.5 wt% linear alkylbenzene sulphonate surfactant and carbonate builder.

Primary alkyl sulfate surfactants

The solid cleaning composition according to the present invention comprises a primary alkyl sulfate surfactant. In the present invention, the term "primary alkyl sulfate surfactant" refers to both the acid form and the neutralized salt form.

Preferably, the primary alkyl sulfate surfactants according to the present invention have the general formula: ROSO₃ ^-M⁺，

Wherein:

r is usually linear C₈To C₂₄An alkyl group which is linear; and

m is a water-soluble cation.

Preferably, R is C₈To C₁₈Alkyl radical, C₁₀-C₁₅Alkyl, more preferably C_10-C₁₄Alkyl, and most preferably C₁₂-C₁₄An alkyl group. R may preferably be C₁₀To C₁₈Alkyl component, more preferably C₁₄To C₁₈Preferably still C₁₂To C₁₅Hydroxyalkyl of the alkyl component. Preferably, the primary alkyl sulfate surfactant has C₈To C₁₈Alkyl chain, more preferably C₈-C₁₆Alkyl chain, and most preferably C₈-C₁₄An alkyl chain. Typically, for laundry applications, C₁₂To C₁₆In particular C₁₄To C₁₆Preferably for lower washing temperatures (e.g., below about 50 ℃), and C₁₆To C₁₈Alkyl chains of (a) are preferred for higher washing temperatures (e.g., above about 50 ℃).

In the general formula of the primary alkyl sulfate surfactant, M is preferably hydrogen or an alkali metal cation selected from sodium, potassium or lithium, more preferably M is sodium. M may also preferably be selected from lithium, calcium and magnesium, ammonium or substituted ammonium (e.g., methyl-, dimethyl-and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.

The primary alkyl sulfate surfactant may be present in the acid form, or the acid form may be neutralized to form a surfactant salt, preferably a water soluble salt form. Typical reagents for neutralization include metal counter ion bases, such as hydroxides, e.g., naOH or KOH. Other suitable agents for neutralizing the acid form of the anionic surfactant include alkaline earth metals, alkali metals, ammonium, ammonia, amines, or alkanolamines (e.g., mono-, di-, and tri-ethanolamines). Non-limiting examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art; suitable alkanolamines include 2-amino-1-propanol, 1-10 aminopropanol, monoisopropanolamine or 1-amino-3-propanol. The amine neutralization may be carried out to a full or partial extent, for example, part of the anionic surfactant mixture may be neutralized with sodium or potassium and part of the anionic surfactant mixture may be neutralized with an amine or alkanolamine.

The solid cleaning composition according to the present invention comprises from 1 wt% to 45 wt% by weight of a primary alkyl sulfate surfactant. Preferably, the solid cleaning composition comprises at least 2 wt.%, at least 4 wt.%, at least 5 wt.%, still preferably at least 6 wt.%, still preferably at least 8 wt.%, most preferably at least 10 wt.% primary alkyl sulfate surfactant, but typically no more than 40 wt.%, still preferably no more than 35 wt.%, most preferably no more than 25 wt.% primary alkyl sulfate surfactant, based on the weight of the solid cleaning composition. More preferably, the solid cleaning composition comprises from 1 wt% to 10 wt%, from 2 wt% to 8 wt%, more preferably from 2 wt% to 6 wt%, most preferably from 2 wt% to 4 wt% of primary alkyl sulfate surfactant by weight.

Alkyl ester fatty acid sulfonate surfactants

The cleaning composition according to the present invention includes an alkyl ester fatty acid sulfonate surfactant.

Preferably, the alkyl ester fatty acid sulfonate surfactant has the general formula:

wherein Ak = predominantly linear C₁₄To C₁₈An alkyl chain.

Preferably, the alkyl ester fatty acid sulfonate surfactant is a methyl ester fatty acid sulfonate surfactant. More preferably, it is C₁₆To C₁₈Sodium methyl sulfonate surfactant (MES). The MES surfactant preferably has a purity of 80 to 90% and 370 to 390g/molSodium salt average molecular weight. Preferably, the alkyl ester fatty acid sulfonate surfactant is sodium neutralized, but may be neutralized with other conventional salts such as potassium and the like. In addition, MES can also be fully or partially neutralized with divalent ions (e.g., magnesium).

The solid cleaning composition according to the present invention comprises from 4 wt% to 45 wt% by weight of an alkyl ester fatty acid sulfonate surfactant. Preferably, the solid cleaning composition comprises at least 5 wt%, more preferably at least 6 wt%, more preferably at least 8 wt%, most preferably at least 10 wt% alkyl ester fatty acid sulfonate surfactant, but typically no more than 40 wt%, more preferably no more than 35 wt%, most preferably no more than 25 wt% alkyl ester fatty acid sulfonate surfactant, based on the weight of the solid cleaning composition. More preferably, the solid cleaning composition comprises from 4 wt% to 10 wt%, preferably from 4 wt% to 8 wt%, and most preferably from 4 wt% to 6 wt% alkyl ester fatty acid sulfonate surfactant by weight. It is highly preferred that the anionic non-soap surfactant according to the invention is predominantly alkyl ester fatty acid sulphonate surfactant, most preferably all anionic non-soap surfactant according to the invention consists of alkyl ester fatty acid sulphonate surfactant.

_{8 18}Water-soluble alkyl carboxylates of C to C fatty acids

The cleaning composition according to the invention comprises C₈To C₁₈Water-soluble alkyl carboxylates of fatty acids.

C₈To C₁₈Water-soluble alkyl carboxylates of fatty acids, also known as "soaps". As used herein, the term soap refers to a carboxylate salt of a fatty acid. Preferably, C₈To C₁₈Water-soluble alkyl carboxylates of fatty acids include alkali metal soaps, e.g., the sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from about 8 to about 18 carbon atoms, preferably from about 8 to about 16 carbon atoms. More preferably 8 to 14 carbon atoms. The fatty acid may preferably be a saturated or unsaturated fatty acid. More preferably saturated.

The fatty acid alkyl carboxylate (soap) content of the composition of the present invention may consist of a single fatty acid alkyl carboxylate (soap compound) or a mixture of fatty acid alkyl carboxylates (soap compound). In some cases, a single fatty acid carboxylate is used. The counter ion may be a single counter ion or a mixture of counter ions.

Suitable counterions are known in the art and include potassium and sodium ions as well as organic amine-based counterions, such as those based on triethanolamine.

The fatty acid carboxylate salt may be unsaturated or saturated. For example, the fatty acid may contain one or more double bonds. Preferably, the soap is greater than 50 wt% unsaturated. The fatty acid may be C₁₀To C₃₀Compounds, e.g. C₁₅To C₂₅A compound is provided. A suitable fatty acid present in the water-soluble alkyl carboxylate is lauric acid. In these cases, the soap is more than 50% by weight of lauric acid carboxylate. For example, it may be a potassium salt. In other words, the soap may exceed 50% by weight of potassium laurate. In some cases, the soap is more than 75 wt% lauric acid carboxylate, e.g., more than 90 wt% or even more than 95 wt%.

The cleaning composition according to the invention comprises 1 to 45 wt.% of C₁₂To C₁₈Water soluble alkyl carboxylates of fatty acids. Preferably, the cleaning composition comprises at least 3 wt.%, more preferably at least 5 wt.%, more preferably at least 8 wt.%, most preferably at least 10 wt.% of C, based on the weight of the cleaning composition₁₂To C₁₈Water-soluble alkyl carboxylate of fatty acid, but generally not more than 40 wt%, more preferably not more than 35 wt%, most preferably not more than 25 wt% of C₁₂To C₁₈Water soluble alkyl carboxylates of fatty acids. It is highly preferred that the composition of the present invention comprises 1 to 10% by weight of C₁₂To C₁₈Water-soluble alkyl carboxylates of fatty acids.

Nonionic surfactant

The cleaning composition according to the present invention comprises a nonionic surfactant.

Suitable nonionic surfactants include the condensation products of aliphatic alcohols having from 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and typically contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 10 to 18 carbon atoms, preferably from 10 to 15 carbon atoms, with from 2 to 18 moles, preferably from 2 to 15, more preferably from 5 to 12, of ethylene oxide per mole of alcohol. Highly preferred nonionic surfactants are the condensation products of Guerbet alcohols with from 2 to 18 moles, preferably from 2 to 15, more preferably from 5 to 12 moles of ethylene oxide per mole of alcohol.

Nonionic surfactants of the amine oxide type, for example, N-coco-N, N-dimethyl amine oxide and N-tallow-N, N-dimethylol amine oxide, and of the fatty acid alkanolamide type, may also be suitable.

Another preferred class of nonionic surfactants which can be used as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Preferred are low-foaming nonionic surfactants. These include, but are not limited to, nonionic surfactants from alkoxylated alcohol groups. Alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18C atoms and an average of 1 to 12 moles of Ethylene Oxide (EO) per mole of alcohol, where the alcohol residues may be linear or methyl-branched, preferably at the 2-position, or may contain linear and methyl-branched residues in the mixture, as are usually present in oxo alcohol (oxo alcohol) residues, are preferably used as nonionic surfactants. In particular, however, alcohol ethoxylates with linear residues, prepared from naturally occurring alcohols having 12 to 18C atoms (e.g. oleyl alcohol), and an average of 2 to 8 moles of EO per mole of alcohol, are preferred. Preferred ethoxylated alcohols include, for example, C with 3EO to 4EO₁₂To C₁₄Alcohol, C with 7EO₉To C₁₂Alcohol, with 3EOC of 5EO, 7EO or 8EO₁₃To C₁₅Alcohols, C with 3EO, 5EO or 7EO₁₂To C₁₈Alcohols and mixtures of these, e.g. C with 3EO₁₂To C₁₄Alcohol with C having 5EO₁₂To C₁₉A mixture of alcohols. The degree of ethoxylation is a statistical average and may be an integer or a fraction for a particular product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols having more than 12EO (ethylene oxide groups) may also be used. Examples of these are primary C with a narrow range of 14EO, 25EO, 30EO, 40EO or 80EO₁₆To C₁₈A source of fatty alcohol. Preferred C with more than 12EO₁₆To C₁₈The fatty alcohol has 60 to 100EO, and more preferably 70 to 90EO. Particularly preferred C with more than 12EO₁₆To C₁₈The fatty alcohol is C with 80EO₁₆To C₁₈A fatty alcohol.

Likewise particular preference is given to using nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols, and in particular from the group of EO-AO-EO nonionic surfactants.

The nonionic surfactant preferably contains a propylene oxide unit in its molecule. Such PO units preferably constitute at most 25 wt%, more preferably at most 20 wt%, and even more preferably at most 15 wt% of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydric alkanols or alkylphenols which additionally comprise polyoxyethylene/polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such nonionic surfactant molecules here preferably constitutes more than 30 wt%, preferably more than 50 wt%, and even more preferably more than 70 wt% of the total molar mass of such nonionic surfactants. Preferred cleaning compositions are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which propylene oxide units constitute at most 25 wt%, more preferably at most 20 wt%, even more preferably at most 15 wt% of the total molar mass of the nonionic surfactant in each molecule.

Preferably, the nonionic surfactant is an alkoxylated nonionic surfactant, particularly ethoxylated primary alcohols and mixtures of these surfactants with surfactants of complex structure, such as polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) surfactants. Such (PO/EO/PO) nonionic surfactants are also characterized by good foam control. Other nonionic surfactants having a melting point above room temperature which are particularly preferably used comprise from 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend comprising 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene (having 17 moles of ethylene oxide and 44 moles of propylene oxide) and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene (initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane).

Nonionic surfactants which have proven particularly preferred for the purposes of the present invention are low-foaming nonionic surfactants comprising alternating ethylene oxide and alkylene oxide units. Of these, surfactants having EO-AO-EO-AO blocks are furthermore preferred, in each case from 1 to 10 EO or AO groups being linked to one another and then being followed by a block of the respective other group. Preferred nonionic surfactants are those of the general formula:

wherein R1 represents a linear or branched, saturated or mono-or polyunsaturated C₆To C₂₄An alkyl or alkenyl residue; each radical R²Or R³Independently of one another from-CH₃、-CH₂CH₃、-CH₂CH₂-CH₃、-CH(CH₃)₂And subscripts w, x, y, z independently of one another represent an integer of 1 to 6.

Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R¹-OH and ethylene oxide or alkylene oxide. Residue R in the above formula¹May vary depending on the source of the alcohol.

Depending on the source used, the residue R¹Containing an even number of carbon atoms and being generally unbranched, preferably from a straight-chain residue of an alcohol having 12 to 18C atoms, e.g. from C₁₂To C₁₄Alcohol formed from a source having C₁₆To C₁₈Of an alcohol having a main C₁₆To C₁₈A narrow range of alcohol sources of carbon atoms or oleyl alcohol. Alcohols available from synthetic sources are, for example, guerbet alcohols or straight-chain and methyl branched residues in methyl branched residues or mixtures at the 2-position, as are typically present in oxo alcohol residues. Regardless of the nature of the alcohol used to prepare the nonionic surfactant contained in the formulation, preferred nonionic surfactants are those wherein R in the above formula¹Denotes those having allyl residues of 6 to 24, more preferably 8 to 20, even more preferably 9 to 15, and still even more preferably 9 to 11 carbon atoms.

In addition to propylene oxide, butylene oxide may be especially considered as alkylene oxide units alternating with ethylene oxide units in the preferred nonionic surfactants.

However, wherein R²Or R³Independently of one another from-CH₂CH₂-CH₃、-CH(CH₃)₂Other alkylene oxides of (a) are also suitable. The nonionic surfactants of the above formula which are preferably used are those wherein R is²Or R³Represents a residue-CH₃W and x represent independently of each other the values 3 or 4 and y and z represent independently of each other those of the values 1 or 2.

Preferred nonionic surfactants are those comprising a C having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units₉To C₁₅Those of alkyl residues.

According to the invention, preference is given to compounds of the formula R¹-CH(OH)CH₂O-(AO)_w-(A'O)_x-(A"O)_y-(A"'O)_z-R²The nonionic surfactant of (1), wherein R¹Or R²Independently of one another, represents straight-chain or branched, saturated or mono-or polyunsaturated C₂To C₄₀An alkyl or alkenyl residue; A. a ', A "and A'" independently of one another denote a signal from the group-CH₂CH₂、-CH₂CH₂-CH₂、-CH₂-H(CH₃)、-CH₂-CH₂-CH₂-CH₂、-CH₂-CH(CH₃)-CH₂-、-CH₂-CH(CH₂-CH₃) A residue of (a); w, x, y and z represent values between 0.5 and 90, wherein x, y and/or z may also be 0.

In particular, preferred end-group-capped poly (alkoxylated) nonionic surfactants are those wherein the surfactant is according to formula R¹O[CH₂CH₂O]_xCH₂CH(OH)R²In addition to the residue R representing a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue having from 2 to 30 carbon atoms, preferably from 4 to 22 carbon atoms¹In addition, it comprises a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue R having from 1 to 30 carbon atoms²X denotes values between 1 and 90, preferably between 30 and 80, in particular between 30 and 60.

Particularly preferred nonionic surfactants are of the formula R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_yCH₂CH(OH)R²Wherein R is¹Represents a straight or branched chain aliphatic hydrocarbon residue having from 4 to 18 carbon atoms or mixtures thereof. R is²Represents a linear or branched hydrocarbon residue having from 2 to 26 carbon atoms or a mixture thereof, x represents a value between 0.5 and 1.5 and y represents a value of at least 15.

A particularly preferred end-group-capped poly (alkoxylated) nonionic surfactant is also of the formula R¹O[CH₂CH₂O]_x[CH₂CH(R³)O]_yCH₂CH(OH)R²Wherein R is¹And R²Independent of each otherRepresents a linear or branched, saturated or mono-or polyunsaturated hydrocarbon residue having from 2 to 26 carbon atoms, R³Independently of one another, from-CH₃、-CH₂CH₃、-CH₂CH₂-CH₃、-CH(CH₃)₂But preferably represents-CH₃And x and y, independently of one another, denote a value between 1 and 32, very particularly preferably with R³＝-CH₃And nonionic surfactants having x values of 15 to 32 and y values of 0.5 and 1.5.

Other useful nonionic surfactants are of the formula R¹O[CH₂CH(R³)O]_x[CH₂]_kCH(OH)[CH₂]_jOR²The terminal-terminated poly (oxyalkylated) nonionic surfactant of (1), wherein R¹And R²Denotes a straight-chain or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue having from 1 to 30 carbon atoms, R³Represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl residue, x represents a value between 1 and 30, k and j represent a value between 1 and 12, preferably between 1 and 5. If the value of x is larger than or equal to 2, then the formula R¹O[CH₂CH(R³)O]_x[CH₂]_kCH(OH)[CH₂]_jOR²Each R in (1)³May be different. R¹And R²Preference is given to straight-chain or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues having from 6 to 22 carbon atoms, particularly preferably residues having from 8 to 18 carbon atoms. For residue R³Particularly preferred are H, -CH₃or-CH₂CH₃. Particularly preferred values of x are in the range of 1 to 20, in particular 6 to 15.

As described above, if x ≧ 2, each R in the above formula³May be different. In this way, the alkylene oxide units in brackets can be changed. For example, if x represents 3, the residue R may be selected³To form ethylene oxide (R)³= H) or propylene oxide (R)³＝CH₃) Units, which may be linked to one another in any order, e.g., (EO) (PO) (EO),(EO) (EO) (PO), (EO) (EO) (EO) (PO), (PO) (PO) (EO) (PO) (PO). The value 3 of x is chosen here as an example and may be entirely larger, the variation range increasing with increasing value of x, for example comprising a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.

Particularly preferred end-capped poly (alkoxylated) alcohols of the above formula have values of k =1 and j =1, so that the above formula is simplified to R¹O[CH₂CH(R³)O]_xCH₂CH(OH)CH₂OR². In the formula, R¹、R²And R³As defined above, x represents a number from 1 to 30, preferably from 1 to 20, and in particular from 6 to 18. Particularly preferred surfactants are those in which the residue R¹And R²Containing 9 to 14C atoms, R³Represent H, and x takes values from 6 to 15.

The C chain length and the degree of ethoxylation or alkoxylation of the above nonionic surfactants are statistical averages which may be whole or fractional for a particular product. Due to the production process, the commercial products of the formula are not essentially composed of individual representatives, but rather of mixtures, so that not only the C-chain length but also the degree of ethoxylation or alkoxylation can be average values and thus fractional numbers.

Another preferred nonionic surfactant is according to the formula:

wherein n is 0 to 5 and m is 10 to 50, more preferably wherein n is 0 to 3 and m is 15 to 40, and even more preferably wherein n is 0 and m is 18 to 25. Such nonionic surfactants are commercially available, for example, under the tradenames Dehypon WET (supplier: BASF) and Genapol EC50 (supplier Clariant).

Another preferred nonionic surfactant is according to the formula:

wherein n is 0 to 5 and m is 10 to 50, more preferably wherein n is 0 to 3 and m is 15 to 40, even more preferably wherein n is 0 and m is 18 to 25;

yet another preferred nonionic surfactant is according to the formula:

wherein n is 0 to 5 and m is 10 to 50, more preferably wherein n is 0 to 3 and m is 15 to 40, and even more preferably wherein n is 0 and m is 18 to 25.

Preferably, the cleaning composition comprises C₁₂To C₁₈An alkoxylated alcohol comprising from 3 to 9 alkylene oxide units per molecule, preferably from 3 to 7 alkylene oxide units per molecule. Preferred nonionic surfactants are Laundrocilin from Clariant, nonionic surfactants with 7EO groups. The composition has 50 to 55 wt% nonionic, 35 to 40 wt% silicate, and a coating having 5 to 10 wt% sodium carbonate.

The cleaning composition according to the present invention comprises from 1 wt% to 45 wt% of a nonionic surfactant, more preferably the composition comprises from 1 wt% to 25 wt%, and still more preferably from 1 wt% to 5 wt% of a nonionic surfactant. Preferably, the cleaning composition comprises at least 2 wt.%, still more preferably at least 4 wt.%, still more preferably at least 6 wt.%, most preferably at least 10 wt.% nonionic surfactant, but typically no more than 40 wt.%, still preferably no more than 35 wt.%, most preferably no more than 25 wt.% nonionic surfactant, based on the weight of the cleaning composition. Most preferably, the cleaning composition comprises from 1 wt% to 3 wt% of a nonionic surfactant.

The solid cleaning composition according to the invention preferably comprises from 1 wt% to 25 wt% of a surfactant comprising a surfactant selected from the group consisting of primary alkyl sulfate surfactants, alkyl ester fatty acidsAn anionic non-soap surfactant of a sulfonate surfactant or mixtures thereof; c₈To C₁₈Water-soluble alkyl carboxylate salts of fatty acids and nonionic surfactants as described above. It is further preferred that the solid cleaning composition comprises from 1 wt% to 20 wt%, further preferably from 1 wt% to 15 wt% of the surfactant content of the solid cleaning composition.

Other surfactants

In addition to the anionic surfactants mentioned above, selected from primary alkyl sulfate surfactants or alkyl fatty ester sulfonate surfactants, C₈To C₁₈In addition to the water-soluble alkyl carboxylate salt of a fatty acid and the nonionic surfactant, the solid cleaning composition according to the present invention may include other surfactants. When present in the cleaning composition, the other anionic surfactant is present in an amount of less than 5 wt.%, still preferably less than 3 wt.%, further preferably less than 2 wt.%, still further preferably less than 1 wt.%, most preferably the solid cleaning composition of the present invention is substantially free of other anionic surfactant.

The composition according to the invention comprises from 0 wt% to 0.5 wt% of linear alkylbenzene sulphonate surfactant. Preferably, the linear alkylbenzene sulfonate surfactant has C₅To C₂₀An alkyl group. The composition preferably comprises from 0 wt% to 0.3 wt% linear alkylbenzene sulfonate surfactant, more preferably the composition has less than 0.2 wt%, still more preferably less than 0.1 wt% linear alkylbenzene sulfonate surfactant, and most preferably the composition is free of any intentionally added linear alkylbenzene sulfonate surfactant.

The other anionic surfactants may include, but are not limited to, anionic sulfonate surfactants. Examples of such other anionic surfactants include alkyl ether sulfates, alkyl Ethoxy Sulfates (AES), alkyl Ethoxy Carboxylates (AEC), secondary Alkyl Sulfates (SAS), and combinations thereof. More preferably, the anionic surfactant is selected from sodium dodecylbenzenesulfonate (Na-LAS), sodium lauryl ether Sulfate (SLE)S) and combinations thereof. Preferably, the cleaning compositions of the present invention comprise less than 5 wt.% of a C selected from having an average degree of ethoxylation in the range of from about 0.1 to about 5 (preferably from about 0.3 to about 4, more preferably from about 0.5 to about 3)₁₀To C₂₀Straight chain alkyl benzene sulfonate, C₁₀To C₂₀Linear or branched alkyl ethoxy sulfates or mixtures thereof.

More preferably, the cleaning compositions of the present invention are substantially free of other anionic surfactants as described above. As used herein, the terms "substantially free", "substantially free" mean that the indicated material is at least not intentionally added to the composition to form part of the composition, or preferably, is not present at analytically detectable levels. It is meant to include compositions in which the indicated material is present only as an impurity in one of the other materials intentionally included. The indicated materials, if any, may be present at a level of less than 1 wt.%, or less than 0.1 wt.%, or less than 0.01 wt.%, or even 0 wt.%, by weight of the cleaning composition.

Carbonate builders

The compositions of the present invention comprise carbonate builders. Examples of carbonate builders include the alkaline earth and alkali metal carbonates as disclosed in German patent application No.2,321,001.

Preferred alkali metal carbonates are sodium carbonate and/or potassium carbonate, with sodium carbonate being particularly preferred. It is further preferred that sodium carbonate constitutes at least 75 wt%, more preferably at least 85 wt%, and even more preferably at least 90 wt% of the total weight of the alkali metal carbonate builder.

The cleaning composition of the present invention preferably comprises from 15 wt% to 50 wt% carbonate builder, more preferably from 30 wt% to 40 wt% carbonate builder. Preferably, the cleaning composition comprises at least 16 wt%, more preferably at least 18 wt%, more preferably at least 20 wt%, most preferably at least 25 wt% of the nonionic surfactant, but typically no more than 45 wt%, more preferably no more than 40 wt%, most preferably no more than 35 wt% of the carbonate builder, based on the weight of the cleaning composition.

Non-carbonate builders

In addition to carbonate builders, the solid cleaning compositions of the present invention may comprise other inorganic non-carbonate builders. Other preferred builders may be selected from silicates, silica, zeolite phosphates or mixtures thereof. While other non-carbonate builders may be organic builders including, but not limited to, salts such as succinates, carboxylates, malonates, polycarboxylates, citric acid or salts thereof. It is highly preferred that the compositions of the present invention are substantially free of phosphate-containing builders. Highly preferably, the composition comprises from 0 wt% to 0.5 wt% phosphate builder, most preferably no deliberately added phosphate builder. Examples of phosphate builders include, but are not limited to, the alkali metal or ammonium salts of tripolyphosphate, pyrophosphate, diphosphate, and orthophosphate.

Suitable silicates include SiO₂∶Na₂Water soluble sodium silicate having an O ratio of 1.0 to 2.8, preferably a ratio of 1.6 to 2.4, and most preferably a ratio of 2.0. The silicate may be in the form of an anhydrous salt or a hydrated salt. SiO 2₂∶Na₂Sodium silicate with an O ratio of 2.0 is the most preferred silicate.

The silicate is preferably present in the detergent composition according to the invention at a level of from 5 wt% to 50 wt%, more preferably from 10 wt% to 40 wt% by weight of the composition.

Water insoluble particles

Preferably the cleaning compositions of the present invention comprise a very limited amount, i.e. up to 2 wt%, of insoluble particulate material other than non-carbonate builders. Such particulate matter may include an abrasive or may even be a silicate such as sodium silicate. The composition may comprise one type of particulate material or a mixture of different particles while still being in the range of up to 2% by weight of the total composition.

Whenever such particles are present, it is preferred that the Moh's index of such particulate matter be in the range of 2.5 to 6.0. The particulate material may be one or more of clay, calcite, dolomite, olivine, feldspar, apatite, fluorite and hematite, kyanite, magnetite, orthoclase and pumice. Such particles, whenever present, have an average particle size of from 0.5pm to 400pm, more preferably from 10pm to 200pm.

Foam inhibitor

The solid detergent composition according to the present invention preferably comprises a foam inhibitor. The foam inhibitor, preferably a non-soap foam inhibitor, is present at a level of from 0.01 wt% to 15 wt%, preferably from 0.02 wt% to 10 wt%, more preferably from 0.05 wt% to 5 wt%, most preferably from 0.5 wt% to 5 wt% of the composition.

Suitable foam inhibitors for use herein may comprise essentially any known antifoam compound, including, for example, silicone antifoam compounds and 2-alkyl alkanol antifoam compounds. Suds suppressors by suds suppressors is herein meant any compound or mixture of compounds which acts to suppress sudsing or sudsing generated by a solution of the detergent composition, particularly in the presence of agitation of the solution.

Particularly preferred foam inhibitors for use herein are silicone foam inhibitors as defined herein such as any antifoam compound including silicone components. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein and generally throughout the industry encompasses a variety of relatively high molecular weight polymers containing siloxane units and various types of hydrocarbon groups. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes having trimethylsilyl end-capping units.

Preferably, the foam inhibitor is a combination of an antifoam compound and silica. In this combination, preferably the defoaming compound is a silicone defoamer compound, most preferably polydimethylsiloxane. In this combination, the antifoam compound is present in an amount of 50 to 99 weight percent, preferably 75 to 95 weight percent, of the foam inhibitor; and the silica is present at a level of from 1 to 50 wt%, preferably from 5 to 25 wt%, based on the weight of the foam inhibitor. Utensil for cleaning buttockThe foam inhibitor with the combination of silica and antifoam compound is incorporated into the detergent composition at a level of from 5 wt% to 50 wt%, preferably from 10 wt% to 40 wt% by weight. Furthermore, the foam inhibitor preferably comprises a dispersant compound, most preferably a silicone glycol comb copolymer (silicone glycol rake copolymer) having a polyoxyalkylene content of 72% to 78% and an ethylene oxide to propylene oxide ratio of 1.9 to 1.1, in an amount of 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol comb copolymer of this type is DCO544, commercially available from DOW corning under the trade name DCO 544; in addition, the foam inhibitor may include an inert carrier fluid compound, most preferably containing C having a degree of ethoxylation of from 5 to 50, preferably from 8 to 15₁₆To C₁₈Ethoxylated alcohol in a content of from 5% to 80%, preferably from 10% to 70%, by weight.

Another preferred foam inhibitor is described in EP-a-0210731 and comprises a combination of a silicone antifoam compound and an organic carrier material having a melting point in the range 50 ℃ to 85 ℃, wherein the organic carrier material comprises a monoglyceride and a fatty acid having a carbon chain of 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or mixtures thereof, and having a melting point of from 45 ℃ to 80 ℃.

Still further examples of foam inhibitors include silicone based foam inhibitors, hydrocarbon foam inhibitors, monostearyl phosphate foam inhibitors, or combinations thereof.

Other highly preferred suds suppressors comprise polydimethylsiloxanes or mixtures of silicones, for example, polydimethylsiloxanes, aluminosilicates and polycarboxylic acid polymers, such as copolymers of maleic and acrylic and monocarboxylic fatty acids.

Form of the composition

The compositions of the present invention may be prepared by a variety of conventional methods known in the art including, but not limited to, mixing of ingredients (including dry blending), compaction (e.g., agglomeration), extrusion, tableting, or spray-drying of the various compounds contained in the detergent components or mixing of these techniques, whereby the compositions herein may also be prepared by, for example, compaction (including extrusion and agglomeration) or spray-drying. The detergent composition may be prepared by any conventional method, with slurry preparation and spray drying techniques being particularly preferred.

The compositions herein may take a variety of physical solid forms, including, for example, in the form of powders, granules, strips, noodles, pastes, tablets, flakes, lozenges, and strips, and preferably the composition is in the form of a powder, granules, or tablets, and also preferably the composition is in the form of a powder. The composition may be in the form of a unit dose formulation, a delayed delivery formulation, a detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to those skilled in the art in view of the teachings herein. The cleaning composition may have a form selected from the group consisting of powder, unit dose or sachet form, tablet, gel, paste, strip or flake. Preferably, the composition is used for hand washing. Preferably, the cleaning composition of the present invention is a laundry detergent composition. Preferably the composition is in the form of a solid. It is further preferred that the composition is in the form of a spray-dried powder.

The composition preferably has a density of greater than 350 g/l, more preferably greater than 450 g/l or even greater than 570 g/l.

pH of the composition

The solid cleaning composition according to the present invention preferably has an alkaline pH, typically in the range of 9 to 11 when measured at 25 ℃ with a10 wt.% dilution of deionized water.

Suitable pH buffering components for use herein are selected from alkali metal salts of carbonic acid, bicarbonic acid, citric acid, citrates, polycarbonic acid, sesquicarbonic acid, silicic acid, polysilicic acid, boric acid, metaboric acid, phosphoric acid, stannic acid, aluminic acid, and mixtures thereof.

Optional ingredients

The cleaning compositions of the present invention may preferably include one or more optional ingredients selected from the group consisting of cleaning and care polymers, enzymes, enzyme stabilizing systems, brighteners, fabric hueing agents, perfumes, and bleaches.

Cleaning polymers

Cleaning polymers include, but are not limited to soil release polymers, carboxylate polymers, anti-redeposition polymers, cellulosic polymers, care polymers, dye transfer inhibition polymers, amphiphilic alkoxylated grease cleaning polymers, clay soil cleaning polymers, soil suspension polymers, or mixtures thereof.

Suitable carboxylate polymers include polymers such as maleate/acrylate random copolymers or polyacrylate homopolymers. Suitable carboxylate polymers include polyacrylate homopolymers having a molecular weight of 4,000da to 9,000da; a maleate/acrylate random copolymer having a molecular weight of from 30,000Da to 100,000Da or from 50,000Da to 100,000Da or from 60,000Da to 80,000Da.

Also suitable are homo-or copolymeric carboxylic acids, for example polyacrylic acid, polymethacrylic acid, polymaleic acid, copolymers of acrylic acid or methacrylic acid with maleic acid and maleic acid with vinylmethylether, which are present in the free acid or preferably in the form of the sodium salt. Preferred representatives of this group are sodium polyacrylates and sodium salts of acrylic acid-maleic acid copolymers (where the weight ratio of acrylic acid: maleic acid is from 10 to 1, preferably from 1 to 2. These compounds generally have a molecular weight of 3,000 to 150,000, preferably 5,000 to 100,000.

Soil release polymers are designed to modify the fabric surface to facilitate soil removal. Typically the soil release polymer is based on derivatives of polyethylene glycol/vinyl acetate copolymers or polyethylene terephthalate polyesters and combinations thereof. Preferred soil release polymers include polymers of aromatic dicarboxylic acids and alkylene glycols (including polyalkylene glycol-containing polymers) as described in WO2009/153184, EP2692842 and WO 2014/019903. Suitable soil release polymers are described by Clariant in

The polymers are sold under a range of polymers such as, for example,

SRN240、

SRN100、

SRN170、

SRN300、

SRN325、

SRA100 and

SRA300. Other suitable soil release polymers are those derived from Rhodia and

the series of polymers sold, for example,

SF2、

SRP6 and

crystal. Preferred polymers are selected from polyester soil release polymers, capped and non-capped sulfonated PET/POET polymers, capped and non-capped non-sulfonated PET/POET polymers, or combinations thereof.

Preferably, the content of these soil release polymers in the auxiliary particles is from 3 wt% to 15 wt%, at least 5 wt%, more preferably at least 6 wt%, still more preferably at least 6.5 wt%, most preferably at least 7 wt%, but typically not more than 14 wt%, still preferably not more than 13 wt%, most preferably not more than 12 wt%.

Antiredeposition polymers are designed to suspend or disperse soils. Typically, the anti-redeposition polymer is a polyethylene glycol polymer, a polycarboxylate polymer, a polyethyleneimine polymer, or mixtures thereof. Preferably, the anti-redeposition polymer is an acrylate polymer, a maleic anhydride polymer, or a copolymer of acrylic acid and maleic acid, and combinations thereof. Such polymers are available from BASF under the trade name

(forms of neutralization) and

(acidic form). Suitable anti-redeposition polymers are ethoxylated and/or propoxylated polyethyleneimine or polycarboxylate materials, for example, acrylic-based homopolymers or copolymers available from Dow Chemical under the trademark ACUSOL, akzonobel under the trademark Alcosperse, or BASF under the trademark Sokolan.

Suitable care polymers include cationically modified or hydrophobically modified cellulosic polymers. Such modified cellulose polymers can provide anti-wear benefits and dye fixing benefits to fabrics during the wash cycle. Suitable cellulosic polymers include cationically modified hydroxyethyl cellulose. Other suitable care polymers include dye fixing polymers, for example, condensation oligomers produced by condensation of imidazole and epichlorohydrin (preferably in a ratio of 1. A suitable commercially available dye fixing polymer is

FDI (Cognis). Preferably, the auxiliary particles comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of the care polymer.

An example of a suitable chelating polymer is DEQUEST^TMAnd the organophosphonate-type chelating polymers and the alkane hydroxy phosphonates sold by Monsanto.

The cleaning composition is preferably substantially free of phosphate-based chelating polymers. Substantially free, as used herein, means that no phosphate-based chelating polymer is intentionally added.

Enzyme:

the compositions of the present invention preferably comprise one or more enzymes. Preferred examples of enzymes include those that provide cleaning performance and/or fabric care benefits.

Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, xyloglucanases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, G-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. Typical combinations are enzyme cocktails that may comprise, for example, proteases and lipases in combination with one or more of amylases, mannanases, and cellulases. When present in a detergent composition, the above additional enzymes may be present at levels of from about 0.00001% to about 2%, from about 0.0001% to about 1%, or from 0.001% to about 0.5% of enzyme protein by weight of the detergent composition.

In one aspect, preferred enzymes include proteases. Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, e.g., subtilisin (EC 3.4.21.62). Suitable proteases include those known to those skilled in the art and preferably from animal, plant or microbial sources. In one aspect, such suitable proteases may be of microbial origin. Suitable proteases include chemically or genetically modified mutants of the above-mentioned suitable proteases. In one aspect, suitable proteases may be serine proteases, such as alkaline microbial proteases or/and trypsin-type proteases. Examples of suitable neutral or alkaline proteases include:

(a) Subtilisins (EC 3.4.21.62), including those derived from Bacillus (Bacillus), for example, bacillus lentus (Bacillus lentus), bacillus alkalophilus (B.alkalophilus), bacillus subtilis (B.subtilis), bacillus amyloliquefaciens (B.amyloliquefaciens), bacillus pumilus (Bacillus pumilus) and Bacillus gibsonii (Bacillus gibsonii).

(b) Trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g., of porcine or bovine origin), including fusarium protease.

(c) Metalloproteinases, including those derived from Bacillus amyloliquefaciens (Bacillus amyloliquefaciens), preferred proteases include those derived from Bacillus gibsonii (Bacillus gibsonii) or Bacillus Lentus (Bacillus Lentus).

Suitable commercially available proteases include Novozymes A/S (Denmark) under the trade name Novozymes A/S

Liquanase

Savinase

And

those sold under the trade name of Genencor International

Purafect

Purafect

10

And Purafect

Those sold under the trade name Solvay Enzymes

And those sold by Optimase.

Suitable alpha-amylases include those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. Preferred alkaline alpha-amylases are derived from a Bacillus strain, e.g.Bacillus licheniformis, bacillus amyloliquefaciens, bacillus stearothermophilus, bacillus subtilis, or other Bacillus species (Bacillus sp.), e.g.Bacillus species NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (U.S. Pat. No. 7,153,818), DSM 12368, DSMZ No.12649, KSM AP1378 (WO 97/00324), KSM K36, or KSM K38 (EP 1,022,334). Preferred amylases include:

a) Variants having substitutions in relation to the 25 enzyme listed in WO 96/23874 as SEQ ID No.2 at one or more of the following positions: 15. 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444.

b) Variants having one or more substitutions in the following positions with respect to the AA560 enzyme listed as SEQ ID No. 12:

26. 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 30 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, preferably also comprising D183^*And G184^*Is absent.

c) Variants exhibiting at least 95% identity with the wild-type enzyme from Bacillus species 707 (SEQ ID NO:7 in US 6,093,562), especially those comprising one or more of the following mutations: m202, M208, S255, R172, and/or M261. Preferably, the amylase comprises one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N, and/or R172Q. Particularly preferred are those comprising the M202L or M202T mutation.

d) Variants exhibiting at least 90% identity with SEQ ID No.4 (wild-type enzyme from Bacillus SP 722) in WO06/002643, in particular variants with deletions at positions 183 and 184 as well as the variants described in WO 00/60060, which are incorporated by reference.

e) The variant described in WO 09/149130, preferably a variant which shows at least 90% identity with SEQ ID NO:1 or SEQ ID NO:2 (wild-type enzyme from Geobacillus stearothermophilus or a truncated form thereof) in WO 09/149130.

Suitable commercially available alpha-amylases include

TERMAMYL

STAINZYME

And

(Novozymes A/S, bagsvaerd, denmark) 15

AT9000Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200Wien Austria、

OPTISIZE HT

And PURASTAR

(Genencor International Inc., palo Alto, calif.) and

(Kao, 14-10Nihonbashi Kayabacho,1-chome, chuo-ku Tokyo 103-8210, japan). In one aspect, suitable amylases include

STAINZYME and STAINZYME

And mixtures thereof.

In one aspect, such enzymes may be selected from: lipases, including "first cycle lipases". In one aspect, the lipase is a first wash lipase, preferably a variant of a wild-type lipase from Thermomyces lanuginosus, comprising one or more of the T231R and N233R mutations. The wild-type sequence is 269 amino acids (amino acids 23-291) from Swissprot accession number Swiss-Prot 059952 (from Thermomyces lanuginosus (Humicola Ianugninosa)). Preferred lipases will include those under the trade name

And

those sold.

In one aspect, other preferred enzymes include microorganism-derived endoglucanases having endo-beta-1, 4-glucanase activity (e.c. 3.2. L4) and mixtures thereof, including bacterial polypeptides endogenous to a member of the genus bacillus having a sequence at least 90%, 94%, 97% and even 99% identical to the amino acid sequence of SEQ ID No.2 in 7,141,403b 2. Suitable endoglucanases are known under the trade name endoglucanase

And

(Novozymes A/S, bagsvaerd, denmark).

Other preferred enzymes include those under the trade name

Pectate lyases sold under the trade name pectate lyase

(all from Novozymes A/S, bagsvaerd, denmark) and

(Genencor International Inc., palo Alto, california).

Enzyme stabilization system

The enzyme-containing compositions described herein may optionally comprise from 0.001% to 10%, in some embodiments from about 0.005% to about 8%, and in other embodiments, from about 0.01% to about 6%, by weight of the composition, of an enzyme stabilization system. The enzyme stabilizing system may be any stabilizing system compatible with detersive enzymes. Such a system may be inherently provided by other formula actives or added separately, for example, by the formulator or by the manufacturer of the detergent-ready enzyme. For example, such stabilizing systems may comprise calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acids, chlorine bleach scavengers, and mixtures thereof, and are designed to address different stabilization issues, depending on the type and physical form of the cleaning composition. In the case of detergent compositions comprising a protease, a reversible protease inhibitor, for example, boron compounds (including borates, 4-formylphenylboronic acid, phenylboronic acid and derivatives thereof) or compounds (such as calcium formate, sodium formate and 1, 2-propanediol) may be added to further improve stability.

Whitening agent

Optical brighteners or other brightening or whitening agents (including fluorescers) can be incorporated at levels of from 0.01% to 1.2% by weight of the composition. Commercial brighteners suitable for use in the present invention can be divided into subgroups, including but not limited to: stilbene, pyrazoline, coumarin, benzoxazole, carboxylic acid, methionin, dibenzothiophene-5, 5-dioxide, azoles, derivatives of 5-and 6-membered ring heterocycles, and other miscellaneous agents. Preferred commercially available whitening agents include Tinopal AMS-GX from Ciba Geigy Corporation, tinopal UNPA-GX from Ciba Geigy Corporation, tinopal 5BM-GX from Ciba Geigy Corporation. These also include DASCC and CBSX. The whitening agent may be added in particulate form or as a premix with a suitable solvent such as a nonionic surfactant, monoethanolamine, propylene glycol.

Fabric toner

The composition may contain a fabric hueing agent (sometimes referred to as a sunscreen, bluing agent, or brightener). Typically, the hueing agent provides a blue or violet hue to the fabric. The toners may be used alone or in combination to create a particular hueing shade and/or to tint different fabric types. This may be provided, for example, by mixing red and green-blue dyes to produce a blue or violet hue. The hueing agent may be selected from any known dye chemistry class, including, but not limited to, acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrazo, polyazo), including 30 premetallized azo, benzodifuran and benzodifuranone, carotenoids, coumarins, anthocyanidins, diaza hemicyanines, diphenylmethane, formazan, hemicyanines, indigotine, methane, naphthalimides, naphthoquinones, nitro and nitroso groups, oxazines, phthalocyanines, pyrazoles, stilbenes, styryls, triarylmethanes, triphenylmethanes, xanthenes, and mixtures thereof. Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments.

Perfume

The solid cleaning composition according to the present invention preferably comprises a perfume. Examples of suitable fragrances include those well known to those skilled in the art. The perfume may be in the form of a free oil, an encapsulated perfume, or a combination thereof.

Bleaching agent

The solid cleaning composition according to the present invention preferably comprises a bleaching agent. Non-limiting examples of bleaching agents suitable for use in the present invention include metal percarbonates (particularly sodium salts), organic peroxyacid bleaches, combinations of organic peroxyacid bleach precursors and hydrogen peroxide sources, and combinations thereof. The compositions of the present invention preferably comprise from 0.1% to 10% by weight of a bleaching agent.

According to a second aspect of the present invention, there is disclosed a process for preparing a solid cleaning composition according to any preceding claim, comprising the steps of:

i) Adding carbonate builder to the mixing chamber;

ii) adding an anionic non-soap anionic surfactant selected from primary alkyl sulphate surfactants, alkyl ester fatty acid sulphonate surfactants or mixtures thereof; c₈To C₁₈A water-soluble alkyl carboxylate salt of a fatty acid, and a nonionic surfactant; from 0 wt% to 0.5 wt% of a linear alkylbenzene sulphonate surfactant, and

iii) Mixing the above ingredients for 2 to 15 minutes to obtain the solid cleaning composition according to the first aspect.

According to a third aspect of the present invention, there is disclosed a method of laundering fabrics using a solid cleaning composition according to any preceding claim, comprising the steps of:

i) Preparing an aqueous wash liquor by adding or dissolving a solid cleaning composition according to the first aspect or prepared according to the second aspect in a liquid, preferably water;

ii) contacting the textile during the washing step of the main wash cycle or hand wash process with a wash liquor, preferably comprising a soaking and cleaning step of the soiled textile in the wash liquor for a predetermined period of time; and

iii) (iii) rinsing the textile from step (ii) in clean water, wherein the rinsing step involves less than 3 rinses, preferably a single rinse.

iv) optionally drying the textile.

According to a fourth aspect of the present invention, anionic non-soap surfactants (selected from primary alkyl sulfate surfactants or alkyl esters) in solid cleaning compositions are disclosedFatty acid sulfonate surfactants or mixtures thereof); c₈To C₁₈Water-soluble alkyl carboxylates of fatty acids; a nonionic surfactant; and the use of a carbonate builder in combination to provide low or no sudsing during a wash process.

The invention will now be illustrated by the following non-limiting examples, in which parts and percentages are by weight unless otherwise indicated.

Examples

Example 1

Preparation of the composition:

a comparative cleaning composition with LAS surfactant (Ex a) having the formulation provided in table 1 was prepared. Two cleaning compositions (Ex 1 and Ex 2) according to the invention were prepared, wherein primary alkyl sulfate, nonionic surfactant and C were prepared as provided in table 1₈To C₁₈Alkyl carboxylates of fatty acids (soaps).

Measurement of foaming Properties of the composition:

a fixed amount of the composition of comparative example ExA was weighed and diluted in 5 liters of water contained in a transparent container to provide a wash liquor having a concentration of 2.5 grams of the composition per liter of water. The hardness of the water used for the preparation of the washing liquid was 24FH (French hardness; ca: mg; 2. The prepared washing solution was vigorously stirred by hand for 20 seconds. Thereafter, the height of the generated foam was measured using a measuring tape. The foam height at this stage (pre-soak stage) was recorded. Foam height data is provided in table 1.

1 kg of a wash load of soiled cotton fabric was added to the wash liquor and the fabric was soaked for 30 minutes. The foam height in the container after soaking the fabric was measured and recorded. Foam height after soaking (after soaking) data is provided in table 1. The soaked fabric was then removed and washed by hand.

The soaked fabric was then rinsed batch wise. 9 liters of clear water were used in each rinse batch. After each rinse, the foam height in the rinse container (rinse phase) was measured and recorded. The data are provided in table 1.

For the solid cleaning compositions of Ex 1 and Ex 2, the procedure described above for hand washing soiled fabrics was similarly followed and the data recorded and provided in table 1 below.

Decontamination study protocol:

a fixed amount of the composition of comparative example Ex a was weighed and diluted in 10.6 liters of clear water contained in a clear container to provide a wash solution having a concentration of 2.5 grams of composition per liter of water. The hardness of the water used for the preparation of the washing liquid was 24FH (French hardness; ca: mg; 2.

2.3Kg of wash load was added to the wash liquor prepared. The wash load consisted of 50% cotton and 50% polyester-cotton fabric. In addition, the size is 10X 10cm²A stain sample of stain type ICS-1 × 1+ ICS-2 × 1+ Grass KCoX1 (from TUV Pvt. Ltd.) is added to the wash liquor along with the wash load. The wash liquor was allowed to stand for a period of 30 minutes to soak the wash load in the wash liquor. Thereafter, the soaked wash load was washed manually and rinsed batch-wise. 1.2 liters of clean rinse water was used for each batch.

Stain removal measurement:

a) Measurement of Stain Release Index (SRI)

Stain Release Index (SRI) is an indicator of the amount of stain present on fabrics removed during a laundering process. The intensity of any stain after washing was measured by reflectometry and expressed as the difference between stained and cleaned fabrics, giving the Δ E per stain^*。

SRI values were calculated after measurements of L, a and b using Artix Scan F1, microtek. It is defined as Δ E^*And calculated as follows:

SRI＝100-ΔE^* _{after washing}

L, a, and b are coordinates of the CIE 1976 (L, a, b) color space, determined using a standard reflectometer. Delta E can be measured before and after washing stains^*Obtaining AE^*bw (before washing) and AE^*aw (after washing).

An SRI of 100 indicates complete stain removal. The higher the SRI value, the greater the stain removal potential. Δ E after washing is the Laa b color space difference between the cleaned (unwashed) fabric and the stain after washing. Thus, a Δ E of zero after washing indicates complete removal of the stain. Therefore, an SRI aw (aw: after washing) of 100 is a completely removed stain. Clean (or virgin) fabric is 25 "absolute standard" which has not been laundered. For each experiment, it refers to a piece of fabric identical to the fabric to which the stain was applied. Thus, its point in L a b color space remains unchanged.

For each composition, the stain removal performance was recorded and provided in table 2.

TABLE 1

* Primary alkyl sulfates from Galaxy Surfactants Ltd.

^#Nonionic particles from Clariant under the trade name Laundroclin NI 111.

^@Soap powder was purchased from JLL.

The data in table 1 show that the compositions prepared according to the invention (Ex 1, ex 2) have a foam height significantly lower than the comparative composition (Ex a) and, moreover, the amount of water required to completely rinse the fabrics washed in the composition according to the invention (9 liters of fresh water) is lower than the comparative compositions (27 to 36 liters of fresh water).

TABLE 2

The table above shows that good stain removal results were obtained for Ex 1 with cleaning compositions within the scope of the invention compared to comparative detergent compositions (comparative Ex a) with higher levels (14 wt%) of LAS surfactant.

Example 2

Solid detergent compositions according to the present invention suitable for use in a drum washing machine were prepared as shown in table 3. Furthermore, a composition according to the invention in which the non-soap anionic surfactant is an alkyl ester fatty acid sulphonate surfactant was prepared and evaluated for foamability according to the method detailed in example 1. Detailed recipe and measured foamability data are included in table 3.

TABLE 3

The data in table 1 show that no sudsing is observed during the main wash cycle when the composition of the present invention is used in a drum washing machine, as compared to the conventional drum composition (Ex B). Furthermore, the hand wash composition (Ex 4) prepared according to the invention with MES as non-soap anionic surfactant showed no foam formation during the soak and rinse stages and required only 9 liters of water for complete rinse and only 1 rinse.

Example 3

The cleaning performance of the detergent composition according to the invention (Ex 3) was evaluated qualitatively by a panel of 8 consumers. Consumers evaluated detergent compositions by washing their daily wash load for 7 days using compositions according to the invention and then washing the next 7 days with their daily customary detergent composition (Ex B). At the end of the evaluation period, feedback from the consumer was collected and the detailed information is summarized in table 4 below.

TABLE 4

Claims (15)

1. A solid cleaning composition comprising:

i) An anionic non-soap surfactant selected from a primary alkyl sulfate surfactant or an alkyl ester fatty acid sulfonate surfactant or mixtures thereof;

ii)C₈to C₁₈Water-soluble alkyl carboxylates of fatty acids;

iii) A nonionic surfactant;

iv) a carbonate builder, and

v) 0 to 0.5 wt% linear alkylbenzene sulphonate surfactant.

2. The solid cleaning composition of claim 1, wherein the composition comprises 20 wt% to 50 wt% carbonate builder.

3. The solid cleaning composition of claim 1, wherein the primary alkyl sulfate surfactant has C₈-C₁₈Alkyl chain, more preferably C₁₄-C₁₈An alkyl chain.

4. The composition of claim 1, wherein the nonionic surfactant is C₁₂To C₁₈An alkoxylated alcohol comprising from 3 to 9 alkylene oxide units per molecule, preferably from 3 to 7 alkylene oxide units per molecule.

5. A composition as claimed in any one of the preceding claims, wherein the composition comprises a non-soap antifoam in an amount in the range 0.5 to 5% by weight of the composition.

6. A composition according to any preceding claim, wherein the composition has a pH of from 9 to 11 when measured by preparing a 10% solution of the composition in demineralised water at 25 ℃.

7. The composition of any of the preceding claims comprising a colorant, dye, hueing dye, pigment, fabric hueing agent, optical brightener, or a combination thereof.

8. A composition according to any preceding claim, comprising a perfume.

9. The composition of any one of the preceding claims, comprising an enzyme.

10. The composition of claim 9, wherein the enzyme is selected from the group consisting of amylase, mannanase, lipase, protease, cellulase, or combinations thereof.

11. A composition according to any preceding claim comprising an anti-redeposition polymer, preferably an acrylate polymer, a maleic anhydride polymer or a copolymer of acrylic acid and maleic acid, or combinations thereof.

12. Composition according to any one of the preceding claims, comprising a soil release polymer, preferably a PET-POET polymer.

13. A composition according to any preceding claim comprising a bleaching agent.

14. A method for reducing the number of rinses during a wash cycle, the method comprising the steps of:

i) Adding a solid cleaning composition according to any of the preceding claims 1 to 10 to water to form a wash liquor;

ii) contacting the textile with the wash liquor during a main wash cycle of a laundry process;

iii) Rinsing the textile with water, wherein the rinsing step comprises less than 3 rinses, preferably a single rinse; and

iv) optionally drying the textile.

15. An anionic non-soap surfactant selected from primary alkyl sulfate surfactants or alkyl ester fatty acid sulfonate surfactants or mixtures thereof in the solid cleaning composition; c₈To C₁₈Water-soluble salts of fatty acids; a nonionic surfactant; and the use of a combination of carbonate builders to provide low or no sudsing during a wash process.