CN100422299C - Detergent composition comprising hydrotrope - Google Patents

Abstract

The present invention relates to detergent compositions, particularly laundry detergent compositions in liquid, granular and tablet form, comprising an improved hydrotrope wherein the hydrotrope is a molecule in which two polar groups are separated by at least An organic molecule with 5 aliphatic carbon atoms separated from each other; liquid compositions containing this hydrotrope possess viscosity, dilution form and dissolution behavior that make the product an effective and convenient liquid laundry detergent composition.

Description

Detergent composition comprising hydrotrope

field of invention

The present invention relates to detergent compositions, particularly laundry detergent compositions in liquid, granular and tablet form, comprising an improved hydrotrope wherein the hydrotrope is a molecule in which two polar groups are separated by at least An organic molecule with 5 aliphatic carbon atoms separated from each other; liquid compositions containing this hydrotrope possess viscosity, dilution form and dissolution behavior that make the product an effective and convenient liquid laundry detergent composition.

Background of the invention

In recent years, the popularity of detergent products other than granular/powdered forms has increased. These different forms include liquid and tablet forms.

Liquid laundry detergent products offer many advantages over dry, powdered or granular laundry detergent products. Liquid laundry detergent products are easy to measure, dissolve quickly in the wash water, and require no sweeping, allowing them to be easily applied as concentrated solutions or dispersions to soiled areas of laundry and typically take up less storage space than granular products . Additionally, liquid laundry detergents may incorporate ingredients in their formulations that deteriorate during the drying operations used in the manufacture of particulate or granular laundry detergent products. Since the use of liquid laundry detergents is generally considered more convenient than granular laundry detergents, they have been found to be well received by consumers.

Despite the advantages of liquid detergent compositions, granular products also retain many advantages. These advantages include performance, formulation capacity, lower packaging costs and higher product stability. The advantages of product stability and formulation capacity derive primarily from the nature of granular blends in which components can be stabilized individually and isolated into granules prior to blending with other granules. This physical separation in the final detergent composition allows the use of potentially unstable raw materials such as bleaches, enzymes, etc. in the composition.

It is well known that detergent compositions can be made into tablet form by compressing granular detergent compositions. Such tablets offer the consumer the convenience of pre-dosing detergent with each wash without the inconvenience and irregularity of not measuring a sufficient amount of granular detergent composition. This product also provides considerable convenience to consumers who wash clothes outside or away from their residence (such as in a self-service laundromat), because such a consumer only needs to deliver the exact amount she or he needs to wash clothes. So much laundry detergent. The detergent composition can be made into tablet form by compressing the detergent granules.

One disadvantage of conventional liquid detergent compositions is the compatibility of the ingredients. Laundry detergent components that are compatible with each other in granular and/or tablet products tend to interact or react with each other in a liquid environment, especially an aqueous liquid environment.

One disadvantage of conventional granular/powder detergent compositions is the relatively poor solvency, dispersal and solubility properties.

One disadvantage of conventional tablet detergent compositions is the manufacture of sufficiently strong and durable tablets to avoid fragmentation during manufacture, shipping and/or storage, while at the same time disintegrating rapidly when the tablets come into contact with wash water way to create conflicts between tablets.

As mentioned above, there is a constant need to supply/formulate liquid detergent compositions which not only have excellent cleaning performance and compositional and physical stability, but also have properties which make them useful and convenient to use as liquid laundry detergents. viscosity, dilution profile and dissolution behavior of detergent compositions; there is a continuing need to supply/formulate granular/powder detergent compositions with improved dissolution, dispersion and solubility properties, While maintaining the inherent formulation adaptability of granular/powder detergents; and there is a constant need to supply/formulate tablet detergent compositions that are robust and durable to resist manufacturing, shipping and/or or breakage during storage, and can also disintegrate rapidly when exposed to wash water, making the composition of the tablet provide a detergency advantage during laundering treatments.

Summary of the invention

The present invention discloses the addition of certain hydrotropes to detergent compositions of the invention, such as aqueous or non-aqueous liquid laundry detergent compositions, granular/powder laundry detergent compositions and/or tablet laundry detergent compositions. agents that provide 1) a liquid detergent product having the viscosity, dilution form, and dissolution behavior that make the product a useful and convenient liquid laundry detergent composition, and/or 2) a granular/powder form Detergent products having improved dispersing, dissolution and/or solubility properties, which reduce the need for surfactants compared to granular/powder detergent products without such hydrotropes, and/or 3) A tablet detergent product in which a hydrotrope is used as a binder, which has improved strength and durability characteristics, and excellent disintegration and dissolution as compared to a tablet detergent product without such a hydrotrope characteristic.

A. Liquid products

Liquid detergent products containing hydrotropes show excellent cleaning performance, excellent compositional and physical stability and good rheological behavior of the product. These defined hydrotropes can most commonly be classified as organic molecules in which two polar groups are separated from each other by at least 5 aliphatic carbon atoms.

Liquid detergent products can be aqueous or non-aqueous. In a preferred aspect of the present invention, non-aqueous liquid detergents are provided comprising a hydrotrope having two polar groups separated from each other by at least 5 aliphatic carbon atoms, and about 49% to about 99.95% by weight of the composition A non-aqueous liquid phase containing a surfactant and from about 1% to about 50% by weight of the composition of particulate material which is substantially insoluble in said liquid phase and selected from the group consisting of peroxygen bleaches, bleach aids , organic detergent builders, inorganic alkali sources and mixtures thereof, and wherein the composition does not contain any quaternary ammonium compounds derived from the following compounds: C _16-18 unsaturated fatty acids, methyldiethanolamine or methyl chloride.

B. Granular/powder products

Granular/powder detergent products containing these hydrotropes show improved dispersion, dissolution and/or solubility properties which reduce Surfactant requirements. These hydrotropes can most generally be classified as organic molecules having a first polar group and a second polar group separated from each other by at least 5 aliphatic carbon atoms.

C. Tablet products

Detergent tablets prepared according to the present invention contain a hydrotrope ("binder"), characterized in that a binder can most commonly be classified as an organic molecule having a first polar group and the second polar group are separated from each other by at least 5 aliphatic carbon atoms. The tablet detergent product exhibits improved strength and durability properties and excellent disintegration and dissolution properties compared to tablet detergent products without such hydrotropes.

All parts, percentages and ratios used herein are expressed as percent by weight unless otherwise specified. The contents of all documents cited in their respective sections are hereby incorporated by reference.

Detailed description of the invention

definition

" Hydrotrope " - "Hydrotrope" as used herein generally means a compound capable of increasing the solubility, preferably water solubility, of certain sparingly soluble organic compounds, more preferably "hydrotrope" is defined below (see SEFriberg and M. Chiu, J: Decentralized Science and Technology, Vol. 9 (Nos. 5 and 6), pp. 443-457, (1988-1989)):

1. Prepare a solution comprising 25% by weight of the particular compound and 75% by weight of water.

2. When the temperature of the solution was 20 degrees Celsius thereafter, octanoic acid was added to the solution, and the ratio of adding was 1.6 times of the special compound weight in the above-mentioned solution. The solution was mixed in a Sotax beaker with a marine propeller stirrer positioned approximately 5 mm above the bottom of the beaker, the mixer set at 200 rpm.

3. If octanoic acid is completely dissolved, ie if the solution contains only one phase, which is the liquid phase, then this particular compound is a hydrotrope.

"Non-aqueous" or "Anhydrous " - As used herein, "non-aqueous" or "anhydrous" are synonymous and both describe liquids in which the free moisture content is less than about 1%.

" Polar Group " - As used herein, "polar group" refers to a functional group that has a permanent electric dipole moment created by local charges on atoms connected by polar bonds. Polar groups can themselves be anionic or uncharged.

" Dissolution " - As used herein, "dissolution" refers to the rate at which a detergent product mixes with water and releases active ingredients in the wash.

" Particulate " - The term "granule" as used herein means the entire size range of a detergent final product or component, or discrete particulates, agglomerates, or granules in a final detergent product or component admixture Full size range. It expressly does not refer to the particle size fraction (ie, describes less than 100% of the entire size range) of any of these types of particles, unless the particle size fraction represents 100% of the discrete particles in the particle admixture. For each type of particulate component in an admixture, the entire size range of discrete particles of that type have the same or substantially similar composition, whether or not the particles are in contact with other particles. For agglomerated components, the agglomerates themselves are considered discrete particles, and each discrete particle may consist of smaller particles and the binder composition.

" Geometric mean particle diameter " - as used herein the phrase "geometric mean particle diameter" means the geometric median diameter of a group of discrete particles, measured by any standard mass-based particle size measurement technique, preferably by drying sieves points to measure.

"Geometric standard deviation" or "range of values" - as used herein the phrase "geometric standard deviation" or "range of values" of a particle size distribution means the geometrical Width, which can be obtained by dividing the ratio of the 84.13th percentile diameter by the 50th percentile diameter in the cumulative distribution (D _{84 13} /D ₅₀ ); see Gotoh et al.: Handbook of Powder Technology, pp. 6-11, Published by Meral Dekker, 1997.

Hydrotrope

The hydrotropes described in this paragraph are an essential component of the detergent compositions of the present invention.

In the present invention, a hydrotrope is added, and the two polar groups in the hydrotrope are separated from each other by at least 5, preferably 6, aliphatic carbon atoms. Examples of polar groups comprising suitable hydrotropes include hydroxyl and carboxyl ions. Particularly preferred hydrotropes are selected from:

1,4-Cyclohexanedimethanol:

1,6-Hexanediol:

1,7 Heptanediol:

and their mixtures.

Also suitable are mixtures of these organic molecules or any number of hydrotrope molecules, such hydrotrope molecules consisting of two polar groups surrounded by at least 5, preferably 6 aliphatic carbons Atoms are isolated from each other. 1,4-Cyclohexanedimethanol can exist in its cis configuration, trans configuration or a mixture of both configurations.

A. Liquid products

The present invention encompasses liquid laundry detergent compositions which may be aqueous or non-aqueous and which are suitable for use in automatic washing machines or in the pretreatment of stains and stains prior to laundering of textiles or fabrics. The liquid laundry detergent compositions of the present invention may comprise a surfactant-rich liquid-phase alone or they may contain both a surfactant-rich liquid-phase and a phase of solid particulates suspended in the liquid phase. Preferably, the surfactant-rich liquid-phase contains the hydrotrope and any organic diluent.

The hydrotropes of the present invention incorporated into the liquid products of the present invention provide the key ingredient in preventing gelation and/or thickening of the liquid detergent compositions described herein.

Gelation has previously been observed in liquid detergent products prepared without the addition of a hydrotrope as defined herein, upon initial exposure of the product to water and upon dilution with water. Without being bound by theory, it is believed that this gelation phenomenon occurs when the surfactant system forms a viscous surfactant phase (typically flake, spherical or hexagonal) at certain surfactant and water concentrations. phase of shape). A correlation has been found between the viscosity of the water mixture product at the critical dilution range at which gelation is observed and the amount of viscous surfactant phase formed.

In a preferred embodiment, the detergent composition is non-aqueous, having a surfactant-rich non-aqueous liquid phase and having a phase of particulate solids suspended in said liquid phase. In this embodiment, the detergent composition will generally comprise from about 49% to 99.95% by weight of the non-aqueous liquid phase comprising the surfactant. More preferably, the liquid phase is comprised of surfactant and will comprise from about 52% to about 98.9% by weight of the composition. Most preferably, the non-aqueous liquid phase will comprise from about 55% to 70% by weight of the composition herein. This surfactant-containing liquid phase will generally have a density of about 0.6 to 1.4 g/cc, more preferably about 0.9 to 1.3 g/cc.

Without being bound by theory, it is believed that the aforementioned hydrotrope prevents the formation of a sticky surfactant phase that can form upon dilution, because the hydrotrope effectively interacts with the ordered structured layer surfactant molecules, breaking them down And promotes the formation of an isotropic low-viscosity surfactant phase.

These hydrotropes also serve the additional function of modifying the rheology of liquid detergent compositions. For example, it is often difficult to incorporate ethoxylated quaternized amine materials into detergent compositions containing anionic surfactants because the ethoxylated quaternized amine materials cause the anionic surfactant to precipitate from the liquid phase out, resulting in a significant thickening of the liquid detergent composition. However, it is highly desirable to incorporate these clay soil remover/anti-redeposition agents in liquid detergent products because they provide significant performance benefits. The present invention discloses that the inclusion of such hydrotropes avoids the precipitation of anionic surfactants and thickening of the composition commonly observed, thereby producing liquid detergent compositions having the desired rheological properties.

The ethoxylated quaternized amine materials are described in more detail below.

Liquid-phase containing surfactant

The liquid phase of the liquid detergent compositions herein is preferably formed by hydrotropes, nonionic and anionic surfactants, and one or more organic diluents.

Organic Diluents - The liquid phase of the detergent compositions herein comprises one or more aqueous or non-aqueous organic diluents as a major component of the liquid phase. The organic diluent used in the present invention can be either a surface-active liquid, ie, a surfactant, or a non-surfactant liquid, referred to herein as a solvent. The term "solvent" as used herein means the non-surfactant liquid portion of the composition. While some of the essential and/or optional components of the present compositions are actually soluble in the "solvent"-containing liquid phase, other components may be present as particulate feedstock dispersed in the "solvent"-containing liquid phase. Thus the term "solvent" means that it is not required that the solvent material is capable of dissolving virtually all components of the added detergent composition.

The surfactant-containing structured liquid phase will generally comprise from about 50% to 90%, more preferably from about 50% to 80%, most preferably from about 55% to 75%, of the liquid diluent component. The liquid phase of the compositions of the present invention will preferably contain both the liquid surfactant and the non-surfactant solvent.

i) Surfactant Liquids - Suitable types of surfactant liquids that may be used to form the liquid phase of the compositions of the present invention include alkoxylated alcohols, ethylene oxide (EO)-propylene oxide (PO) block polymers substances, polyhydroxy fatty acid amides, alkyl polysaccharides, etc. These typical liquid surfactants are those having an HLB in the range of 10-16. The most preferred surfactant liquids are alcohol alkoxylated nonionic surfactants.

Alcohol alkoxylates are raw materials that conform to the general chemical formula:

R ¹ (C _m H _2m O) _n OH

wherein R ¹ is C ₈ -C ₁₆ alkyl, m is 2-4, and n is in the range of about 2-12. Preferably ^R1 is an alkyl group, which may be primary or secondary, containing about 9 to 15 carbon atoms, more preferably about 10 to 14 carbon atoms. Also preferred as starting materials for ethoxylation are alkoxylated fatty alcohols containing from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule part.

Alkoxylated fatty alcohol feedstocks useful in the liquid phase often have a hydrophilic-lipophilic balance (HLB) in the range of about 3-17. More preferably the feedstock will have an HLB in the range of about 6-15, most preferably about 8-15.

Examples of fatty alcohol alkoxylates useful in or as the liquid phase of the compositions of the present invention would include those produced from alcohols having 12 to 15 carbon atoms and containing about 7 moles of ethylene oxide. These materials are commercially available from Shell Chemical Company under the tradenames Neodol 25-7 and Neodol 23-6.5. Other useful Neodols include Neodol 1-5, which is an ethoxylated fatty alcohol with an average of 11 carbon atoms in its alkyl chain and about 5 moles of ethylene oxide; Neodol 23-9, which is an ethoxylated fatty alcohol with about 9 moles of epoxy ethoxylated C ₁₂ -C ₁₃ primary alcohols with ethane; and Neodol 91-10, which is an ethoxylated C ₉ -C ₁₁ primary alcohols with about 10 moles of ethylene oxide. Ethoxylates of alcohols of this type are also sold under the trade name Dobanol by Shell Chemical Company. Dobanol 91-5 is an ethoxylated C ₉ -C ₁₁ fatty alcohol with an average of 5 moles of ethylene oxide per molecule of fatty alcohol; and Dobanol 25-7 is an ethoxylated C ₁₂ -C ₁₅ fatty alcohol with Molecular fatty alcohols carry an average of 7 moles of ethylene oxide.

Examples of other suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9, both linear secondary alcohol ethoxylates, which are commercially available from Union Carbide Corporation. The former is a mixed ethoxylation product of C ₁₁ -C ₁₅ linear alkane secondary alcohols and 7 moles of ethylene oxide, and the latter is a similar product reacted with 9 moles of ethylene oxide.

Other types of alcohol ethoxylates useful in the compositions of the present invention are higher molecular weight nonionic compounds such as Neodol 45-11, which is the condensation product of similar higher aliphatic alcohols and ethylene oxide, wherein the higher aliphatic Alcohols have 14-15 carbon atoms and about 11 oxirane groups per mole. Such products are commercially available from Shell Chemical Company.

If alcohol alkoxylated nonionic surfactants are employed as part of the liquid phase in the detergent compositions herein, they are preferably present at a level of from about 1% to about 60% of the structural liquid phase of the composition. More preferably, the structured liquid phase will comprise from about 5% to 40% alcohol alkoxylate component. Most preferably, the structured liquid phase of the detergent composition will comprise from about 5% to about 35% of the alcohol alkoxylate component. The concentration of alcohol alkoxylate used in the liquid phase corresponds to the concentration of alcohol alkoxylate in the total composition, which is about 1% to 60% by weight of the composition, more preferably about 2% to 40% by weight, and Most preferably about 5% to 25% by weight.

Other types of surfactant liquids that can be used in the present invention are ethylene oxide (EO)-propylene oxide (PO) block polymers. Materials of this type are well known nonionic surfactants which are commercially available under the tradename Pluronic. These materials are formed by adding segments of ethylene oxide moieties to the ends of polypropylene glycol chains to adjust the surface active properties of the resulting block polymers. EO-PO block polymer nonionic surfactants of this type are described in great detail in Synthetic Detergents, 7th Edition, pp. 34-36 and 189-191 by Davidsohn and Milwidsky and in U.S. Patent Nos. 2,674,619 and 2,677,700 , Synthetic Detergents, published by Longman Science and Technology Press (1987). The contents of all of these publications are incorporated herein by reference. These Pluronic-type nonionic surfactants are also believed to act as effective suspending agents for the particulate materials dispersed in the liquid phase of the detergent compositions herein.

Additional types of surfactant liquids which may be useful in the present compositions include polyhydroxy fatty acid amide surfactants. This type of nonionic surfactant is a material with the following chemical formula:

Wherein R is a C _9-17 alkyl or alkenyl group, p is 1-6, and Z is a sugar group derived from a reducing sugar or an alkoxylated derivative thereof. These materials include C ₁₂ -C ₁₈ N-methyl glucamides. Examples are N-methyl-N-1-deoxyglycosylcocamide and N-methyl-N-1-deoxyglycosyloleamide. Methods of making polyhydroxy fatty acids, amides are known and can be found, for example, in US Patent 2,965,576 to Wilson and US Patent 2,703,798 to Schwartz, the contents of which are incorporated herein by reference. These materials themselves and their preparation are also described in great detail in Honsa, US Patent 5,174,937, issued December 26, 1992, also incorporated herein by reference.

The detergent compositions of the present invention may also contain anionic, cationic and/or amphoteric surfactants. In preferred embodiments, wherein the liquid phase is non-aqueous, the liquid phase is prepared by combining a non-aqueous organic liquid diluent described herein with a surfactant, in the non-aqueous - The addition of such surfactant structures is usually, but not necessarily, optional in the aqueous liquid phase. Structural surfactants may be anionic, nonionic, cationic and/or amphoteric. The surfactants described below may thus be added individually for their surface-active properties or for these properties and their structural properties.

Preferred surfactants are anionic surfactants such as alkyl sulfates, alkyl polyalkoxy sulfates and linear alkylbenzene sulfonates. Another class of common anionic surfactant materials which may optionally be added as a make-up component to detergent compositions comprises carboxyl-type anionic surfactants. Carboxyl-type anionic surfactants include C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (especially ethoxy carboxylates with 1 to 5 EO) and C ₁₀ -C ₁₈ sarcosinates, especially Oleoyl sarcosinate. Another class of common anionic surfactant materials that can be used as a make-up component includes other sulfonated anionic surfactants such as C ₈ -C ₁₈ paraffin sulfonates and C ₈ -C ₁₈ olefin sulfonates. Typically from about 1% to about 30% structured anionic surfactant will be included herein by weight of the composition.

As indicated, one preferred class of structured anionic surfactants comprises primary or secondary alkyl sulfate anionic surfactants. These surfactants are those produced by the sulphation of higher _C8 - _C20 fatty alcohols.

Conventional primary alkyl sulfate surfactants have the general chemical formula:

ROSO ₃ ^- M ⁺

wherein R is a typically linear C ₈ -C ₂₀ hydrocarbon group, which may be straight or branched, and M is a water-soluble cation. Preferably R is C _10-14 alkyl, and M is alkali metal. Most preferably R is about _C12 and M is sodium.

As noted above, conventional secondary alkyl sulfates may also be used as structural anionic surfactants in the liquid phase of the present compositions.

If used, the alkyl sulfate will generally comprise from about 1% to 30% by weight of the composition, more preferably from about 5% to 25% by weight of the composition. Non-aqueous liquid detergent compositions containing alkyl sulfates, peroxygen bleaches, and bleach aids are described in great detail in WO 96/10073 by Kong-Chan et al., published April 4, 1996 , the contents of which are incorporated herein by reference.

Another preferred class of anionic surfactant materials includes alkyl polyalkoxy sulfates which may optionally be added as make-up components to the non-aqueous cleaning compositions of the present invention. Known alkyl polyalkoxy sulfates such as alkoxylated alkyl sulfates or alkyl ether sulfates. Such starting materials conform to the following chemical formula:

R ² -O-(C _m H _2m O) _n -SO ₃ M

wherein R ² is C ₁₀ -C ₂₂ alkyl, m is 2-4, n is about 1-15, and M is a salt-forming cation. Preferably ^R2 is _C12 - _C18 alkyl, m is 2, n is about 1-10, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium. Most preferably ^R2 is _C12 - _C16 , m is 2, n is about 1-6, and M is sodium. Ammonium, alkylammonium and alkanolammonium counterions are preferably avoided when used in the compositions because of incompatibility with peroxygen bleaches.

If used, the alkyl polyalkoxy sulfate will typically comprise from about 1% to 30% by weight of the composition, more preferably from about 5% to 25% by weight of the composition. Non-aqueous liquid detergent compositions containing alkyl polyalkoxy sulfates and polyhydroxy fatty acid amides are described in great detail in PCT Application No. PCT/US96/04223 by Boutique et al., the contents of which are incorporated herein by reference .

The most preferred class of anionic surfactants for use as a make-up component in the present compositions include linear alkylbenzene sulfonate (LAS) surfactants. In particular, such LAS surfactants can be formulated as special types of anionic surfactant-containing powders which are especially suitable for incorporation into non-aqueous liquid detergent compositions of the present invention. Such powders contain two distinct phases. One of the two phases is insoluble in the non-aqueous organic liquid diluent used in the composition; the other phase is soluble in the non-aqueous organic liquid. It is this insoluble phase of the powder containing the preferred anionic surfactant which can be dispersed in the non-aqueous liquid phase of the preferred composition to form a network of aggregated small particles which allows the stabilization of other additional solid particulate materials in the final product suspended in the composition.

Further discussion of suitable surfactants and methods of preparing such surfactants can be found in co-pending application by Jay I. Preparation of Non-Aqueous Liquid Detergent Compositions Containing Particulates", P&G Docket No. 6150, Serial No. 09/202,964, filed December 23, 1998, which is hereby incorporated by reference.

Typically, the liquid phase of the compositions of the present invention will contain from about 25% to about 70% liquid surfactant. More preferably, the structured liquid phase will contain about 30% to 65% liquid surfactant. This corresponds to a concentration of liquid surfactant in the total composition of about 10% to 70% by weight of the composition, more preferably about 20% to 50% by weight of the composition. The total amount of liquid surfactant in the non-aqueous liquid phase of the preferred surfactant structure is as above, and will be further determined according to the type and amount of other components of the composition and according to the desired characteristics of the composition .

ii) Non-surfactant Organic Solvents - The liquid phase of the detergent compositions may also contain one or more non-surfactant organic solvents. Such non-surfactant liquids are preferably those of low polarity. For purposes of the present invention, a "low-polar" liquid is one that has little, if any, tendency to dissolve one preferred type of particulate material used in the present composition, i.e. peroxygen bleach Sodium perborate or sodium percarbonate. It is therefore preferred not to use relatively polar solvents such as ethanol. Suitable types of low-polarity solvents useful in the liquid detergent compositions do include alkylene glycol mono-lower alkyl ethers, low molecular weight polyethylene glycols, low molecular weight methyl esters and amides, and the like.

Preferred types of low-polarity solvents for use in the present compositions include _C4 - _C8 branched or linear alkylene glycols. Feedstocks of this type include hexanediol (4-methyl-2,4-pentanediol), 1,3-butanediol and 1,4-butanediol.

Another preferred class of low-polarity solvents for use herein includes mono-, di-, tri-, or tetra- _C2 - _C3 alkylene glycol mono _C2 - _C6 alkyl ethers. Specific examples of these compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether. Particular preference is given to diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether and butoxy-propoxy-propanol (BPP). Such compounds are commercially available under the tradenames Dowanol, Carbitol, and Cellosolve.

Another preferred type of low-polar organic solvent useful herein includes low molecular weight polyethylene glycol (PEG). These materials have a molecular weight of at least about 150. Most preferred are PEGs with a molecular weight in the range of about 200-600.

Another preferred class of non-polar solvents includes low molecular weight methyl esters. The general chemical formula of this material is: R ¹ -C(O)-OCH ₃ , where R ¹ ranges from 1 to about 18. Suitable examples of low molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.

Of course, commonly used low-polarity non-surfactant organic solvents must be compatible and non-reactive with other composition components used in liquid detergent compositions, such as bleaches and/or activators. Preferably, such solvent components are used in an amount of about 1% to 70% by weight of the liquid phase. More preferably the structured liquid phase will comprise from about 10% to 60% by weight of the low-polarity, non-surfactant solvent, most preferably from about 20% to 50% by weight of the structured liquid phase of the composition. These use concentrations of non-surfactant solvent in the liquid phase correspond to concentrations of non-surfactant solvent in the total composition of about 1% to 50% by weight of the composition, more preferably about 5% to 40% by weight %, and most preferably about 10% to 30% by weight.

iii) Blends of surfactants and non-surfactant solvents - in preferred embodiments using both non-aqueous surfactant liquids and non-aqueous, non-surfactant solvents, containing structured surfactant The ratio of surfactant to non-surfactant liquid in the liquid phase of the agent, for example the ratio of alcohol alkoxylates to low polarity solvents, can be used to modify the rheological properties of the final detergent composition. Generally, the weight ratio of surfactant liquid to non-surfactant organic solvent will be in the range of about 50:1 to 1:50. More preferably the ratio will be in the range of about 3:1 to 1:3, most preferably about 2:1 to 1:2.

solid particulate raw material

In addition to the surfactant-containing liquid phase, the liquid detergent compositions of the present invention preferably comprise from about 1% to 50% by weight, more preferably from about 29% to 44% by weight, of additional dispersed and suspended in the liquid phase. Solid phase particulate raw material. Typically such particulate material will range in size from about 0.1 to 1500 microns, more preferably from about 0.1 to 900 microns. Most preferably the size of such material will be in the range of about 5 to 200 microns.

The additional particulate material used herein may comprise one or more types of detergent composition components in particulate form which are substantially insoluble in the liquid phase of the composition. These materials include peroxygen bleaches, bleach aids, organic detergent builders, inorganic sources of alkalinity and mixtures thereof. The types of particulate materials that may be utilized are described in detail below, although some materials may optionally be included in the particulate component or in the surfactant-containing liquid phase.

In a preferred embodiment, the particulate materials include dye transfer inhibitor PVNO (see above for details), aluminosilicate detergent builders, and other smaller particulate components.

(a) Bleaching Agents with Optional Bleach Builders - The most preferred type of particulate material useful in the present detergent compositions comprises peroxygen bleach granules. Such peroxygen bleaches can be organic or inorganic in nature. Inorganic peroxygen bleaches are often used in combination with bleach aids.

Useful organic peroxygen bleaches include percarboxylic acid bleaches and their salts. Suitable examples of such agents include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, 4-nonylamino-4-oxoperoxybutanoic acid and diperoxydodecanedioic acid. Such bleaching agents have been described in U.S. Patent 4,483,781 to Hartman, published November 20, 1984; European Patent Application EP-A 133,354, published February 20, 1985, by Banks et al.; and Chung et al., published November 1, 1983 disclosed in US Patent 4,412,934. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA), described in Burus et al., US Patent 4,634,551, issued January 6,1987.

Inorganic peroxygen bleaches can also be used in particulate form in the detergent compositions herein. Practically inorganic bleaches are preferred. Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials, most preferably percarbonate. For example sodium perborate (eg mono- or tetra-hydrate) may be used. Suitable inorganic bleaches may also include peroxyhydrates of sodium or potassium carbonate salts and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide . Persulfate bleaches (eg, OXONE, commercially available from DuPont Corporation) can also be used. Inorganic peroxygen bleaches are often coated with silicates, borates, sulfates or water-soluble surfactants. For example, coated percarbonate particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.

Inorganic peroxygen bleaches such as perborates, percarbonates, etc. are preferably combined with bleaching aids, which allow in situ (i.e. during fabric laundering/bleaching using the present composition) generation and aiding in aqueous solution. The corresponding peracid of the bleach. Various non-limiting examples of bleach aids are disclosed in US Pat. Typical bleach aids are nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED). Mixtures thereof may also be used. For other typical bleaches and bleach aids useful herein see US Patent 4,634,551, cited above.

Other useful ones are described in U.S. Patent 5,891,838 issued April 6, 1999 by Angell et al; Amide derived bleach aids, P&G Case No. 7173P, Serial No. 60/088,170, filed June 5, 1998, both of which are incorporated herein by reference.

If peroxygen bleaches are used as all or part of the additional particulate material, they will generally comprise from about 1% to about 30% by weight of the composition. More preferably, peroxygen bleach will comprise from about 1% to about 20% by weight of the composition. Most preferably, peroxygen bleach will be present at a level of about 5% to 20% by weight of the composition. Bleach aids, if used, may comprise from about 0.5% to 20%, more preferably from about 3% to 10%, by weight of the composition. Typically, bleach aids are used to the extent that the molar ratio of bleach to bleach aid is in the range of about 1:1 to 10:1, more preferably about 1.5:1 to 5:1.

(b) Transition Metal Bleach Catalysts -Another class of additional particulate materials which may be suspended in the present liquid detergent compositions include transition metal bleach catalysts which promote the catalytic oxidation of soils and stains on fabric surfaces. The compound is present in a catalytically effective amount, preferably from about 1 ppb to about 99.9%, more typically from about 0.001 ppm to about 49%, preferably from about 0.05 ppm to about 500 ppm (wherein "ppb" means ten percent by weight) of the laundry detergent composition. Parts per billion, and "ppm" means parts per million by weight). Transition-metal bleach catalysts include those selected from Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co( II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr( IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W( Complexes of V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV) coordinated by transition metals and macrocyclic polycyclic rigid ligands, preferably cross-bridged A macrocyclic polycyclic ligand having at least 4 ligand atoms, at least two of which are bridgehead ligand atoms. These catalysts are discussed in great detail and precisely in co-pending provisional application titled "Catalyst and Process for Catalytic Oxidation" by Daryle H. Busch et al., P&G Docket No. 6524P, Serial No. 60/040,629, The contents thereof are incorporated herein by reference.

(c) Organic Detergency Builder Materials - Another class of additional particulate materials that can be suspended in the present liquid detergent compositions include organic detergent builder materials to counteract the harshness encountered during washing/bleaching using the present compositions. Effect of calcium, or other ions, on water hardness. Examples of such materials include alkali metals, citrates, succinates, malonates, fatty acids, carboxymethylsuccinates, carboxylates, polycarboxylates and polyacetylcarboxylates. Specific examples include the sodium, potassium and lithium salts of oxyacidsuccinic acid, mellitic acid, benzene polycarboxylic acids and citric acid. Other examples of organic phosphonate-type chelating agents are the compounds sold by Monsanto under the tradename Dequest and alkylhydroxyphosphonates. Very preferred is citrate.

Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. Examples of such materials include suitable polyacrylic acid, polymaleic acid, and polyacrylic acid/polymaleic acid copolymers and their salts, such as the Sokalan trademark compounds sold by BASF, in the molecular weight range of about 5,000 ~100,000.

Another suitable class of organic detergency builders includes water-soluble salts of higher fatty acids, ie "soaps". Soaps include alkali metal soaps such as the sodium, potassium, ammonium and alkanol ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms. Soap can be prepared by direct saponification of fats and oils or neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and tallow, ie sodium or potassium tallow soap and coconut soap.

If used as all or part of the additional particulate material, the insoluble organic detergent builder herein may generally comprise from about 2% to 20% by weight of the composition, more preferably such builder material may comprise from about 4% to 20% by weight of the composition. 10%.

(d) Inorganic Sources of Alkalinity -Another possible type of additional particulate material that may be suspended in the present liquid detergent compositions may include a material such that the aqueous wash solutions formed from such compositions are generally alkaline in nature. Such materials may or may not function as detergent builders, but rather as raw materials that can counteract the detrimental effect of water hardness on detergency performance.

Examples of suitable alkali sources include water-soluble alkali metal carbonates, bicarbonates, borates, silicates, and (meta)silicates. Although not preferred for ecological reasons, water-soluble phosphate can also be used as a source of alkalinity. Phosphates include alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Of all these alkali sources, alkali metal carbonates such as sodium carbonate are most preferred.

The source of alkalinity, if in the form of a hydratable salt, can also be used as a drying agent in the present liquid detergent compositions. Also the presence of an alkalinity source for the desiccant can provide the benefit of chemically stabilizing composition components which are susceptible to failure by water, such as peroxygen bleach.

If used as all or part of the additional particulate material component, the source of alkalinity herein will generally comprise from about 1% to about 25% by weight of the composition. More preferably, the source of alkalinity may comprise from about 2% to about 15% by weight of the composition. Although these materials are water-soluble, they will generally not be soluble in the non-aqueous detergent compositions described herein.

As noted hereinafter, the aqueous and non-aqueous liquid detergent compositions of the present invention may be in the form of bleach and/or other materials suspended and dispersed in the form of solid particulates throughout a surfactant-containing, preferably structured, The form in the non-aqueous liquid phase is preferred. Typically the structured non-aqueous liquid phase will comprise from about 49% to 99.95% by weight of the composition, more preferably from about 52% to 98.5%, and the dispersed additional solid material will comprise from about 1% to 50% by weight of the composition, more preferably It is about 29% to 44%.

Very small amounts of water can be incorporated into the particulate-containing non-aqueous liquid detergent compositions of this embodiment. In these embodiments, however, the amount of free water herein should in no way exceed about 1% by weight of the composition. More preferably, the water content of the non-aqueous detergent compositions herein will be less than about 1% by weight.

As disclosed herein, the compositions of the present invention are also useful in forming aqueous laundry detergent compositions. Suitable additional ingredients for use in aqueous liquid laundry detergent compositions can be found in US Patent No. 5,783,548 to Fredj et al. and US Patent No. 5,648,327 to Smerznak et al.

The non-aqueous liquid detergent compositions herein containing the microparticles will be relatively viscous and phase stable in the commercial marketplace and under the conditions under which these compositions are used. Typically the viscosity of the present compositions will range from about 300 to 8,000 cps, more preferably from about 1000 to 4,000 cps. For the purposes of the present invention, viscosity is measured with a Carrimed CSL2 rheometer at a shear rate of 20 s ^-1 .

The preparation of non-aqueous liquid detergent compositions is discussed in detail in the co-pending application of Jay I. Kahn et al., entitled "Non-aqueous particulate-containing liquid Preparation of Detergent Compositions," P&G Case No. 6150, Serial No. 09/202,964, filed December 23, 1998, the contents of which are incorporated herein by reference.

An effective amount of the present liquid detergent compositions is added to water to form an aqueous wash/bleach solution in an amount sufficient to form an aqueous solution containing from about 500 to 10,000 ppm of the composition. More preferably, about 800-8,000 ppm of the present detergent compositions are provided in the aqueous wash/bleach solution.

B. Granular/powder products

Granular/powder detergent products of the present invention preferably comprise, in addition to one or more hydrotropes, one or more of the following preferred ingredients, and one or more optional conventional detergent additive materials. These conventional additive materials may include one or more of the solid particulate materials described above in the liquid product section or in the conventional detergent additive materials section below.

While it is well known that hydrotropes can be used to provide the desired phase formation and product viscosity, there has been no previous publication of the use of these organic molecules as hydrotropes to prevent gelation and/or thickening of the detergent compositions described herein. , and thereby improve the dissolution and dispersion properties of granular detergent products. Gelation has previously been observed in detergent products prepared without the addition of a hydrotrope as defined in the present invention when the product was initially exposed to water and diluted with water.

Without wishing to be bound by theory, it is believed that this gelation phenomenon is produced by particles containing surfactants, which either form viscous particles when in contact with water at a certain concentration of surfactant in the wash-liquor or wash-water. Surfactant phases (typically platelets, spheres or hexagons), or form internally-connected "micelle-gels". A correlation has been found between the viscosity of the product-water mixture in the critical dilution range at which gelation is observed, and the amount of viscous surfactant phase formed in that range.

A particularly pronounced problem arises in those areas where fabrics are washed in relatively cold wash water or in automatic washing machines with gentle agitation (as in Japan). At relatively cool wash-water temperatures, a typical aqueous surfactant phase diagram shows a stable region of high-viscosity neat or gelled surfactant phase. And the agitator did not impart enough mechanical energy to disrupt the formation of these high-viscosity phases under mild agitation.

The granular detergent compositions described herein can be either in the form of a single granule or in the form of multiple granules, each having its own composition. When the detergent consists of multiple detergent granules, it is preferred that the above-mentioned organic hydrotrope is contained in the surfactant-rich granules or is coated on the surface of these granules.

preferred ingredients

Detersive Surfactants - Anionic surfactants useful herein are divided into alkyl sulfate surfactants which are separated from the electrolyte in detergent compositions according to the present invention, and the remaining anionic surfactants which are formulated as individual particles. For the purposes of the present invention, alkyl sulfates are defined as alkyl sulfates, alkyl alkoxy sulfates, alkyl sulfonates, alkyl alkoxy carboxylates, alkyl alkoxylated sulfates, and the remaining anionic surfactants are selected from the group consisting of alkylbenzene sulfonates, alpha-olefin sulfonates, paraffin sulfonates, alkyl ester sulfonates, sarcosinates, taurates, and mixtures thereof.

Anionic surfactants, if present, will typically be present in effective amounts throughout the detergent compositions. More preferably, the composition will contain at least about 0.5%, more preferably at least about 5%, even more preferably at least about 10%, by weight of said composition, of anionic surfactant. The composition will also preferably contain no more than about 90% by weight of the composition, more preferably no more than about 50% by weight of the composition, even more preferably no more than about 50% by weight of the composition 30% anionic surfactants.

Provides excellent all-around cleaning power on its own and good grease/oil cleaning over a wide range of temperatures, wash concentrations and wash times, especially when combined with polyhydroxy fatty acid amides (see below), can Dissolved alkyl sulfates, and alkyl sulfate surfactants having improved formulation properties in liquid detergent formulations are water-soluble salts or acids of the formula ROSO ₃ M, wherein R is preferably a C10-C24 hydrocarbyl group , preferably an alkyl or hydroxyalkyl group having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl group; and M is H or a cation such as an alkali (Group IA) metal cation (such as sodium, potassium, lithium ), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethylammonium and quaternary ammonium cations such as tetramethyl-ammonium and dimethylpiperidinium salts, and from alkanolamines Such as ethanolamine, diethanolamine, triethanolamine and cations derived from their mixtures. Typically, _C12-16 alkyl chains are preferred for lower wash temperatures (e.g., below about 50°C), and _C16-18 alkyl chains for higher wash temperatures (e.g., above about 50°C). is preferred.

Another class of suitable alkyl sulfate surfactants according to the invention is the secondary (2,3) alkyl sulfates. These surfactants are preferably of the formula:

wherein x and (y+1) are integers of at least about 7, preferably at least about 9. Preferably these surfactants contain 10 to 18 carbon atoms. US Patent 3,234,258 issued February 8, 1966 to Morris, US Patent 5,075,041 issued December 24, 1991 to Lutz, US Patent 5,349,101 issued September 20, 1994 to Lutz et al., and 1995 to Prieto Suitable examples of such anionic surfactants are disclosed in US Patent 5,389,277, issued February 14, the disclosure of each patent is incorporated herein by reference.

Another class of alkyl sulfate surfactants suitable according to the invention are alkyl alkoxylated sulfates. These surfactants are water-soluble salts or acids, typically of the formula RO(A)mSO ₃ M, wherein R is an unsubstituted C10-C24 alkyl or a hydroxyalkyl group having a C10-C24 alkyl component, Preferably C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl; A is an ethoxy or propoxy unit; m is greater than zero, typically from about 0.5 to about 6, more preferably from about 0.5 to about 3; and M is H or a cation, which can be, for example, a metal cation (eg, sodium, potassium, lithium, etc.), ammonium or substituted-ammonium cation. Desired herein are alkyl ethoxylated sulfates and alkyl propoxylated sulfates. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations such as tetramethyl-ammonium, dimethylpiperidinium salts, and alkanolamines such as monoethanolamine, Cations derived from diethanolamine, and triethanolamine, and mixtures thereof. Exemplary surfactants are C12-C18 alkyl polyethoxylated (1.0) sulfate, C12-C18 alkyl polyethoxylated (2.25) sulfate, C12-C18 alkyl polyethoxylated ( 3.0) sulfates, and C12-C18 alkyl polyethoxylated (4.0) sulfates, wherein M is conveniently selected from sodium and potassium. The surfactants used herein can be made from natural or synthetic alcohol starting materials. Chain length represents the average hydrocarbon chain distribution including branches. The anionic surfactant component may include alkyl sulfates and alkyl ether sulfates derived from conventional alcohol sources such as natural alcohols and synthetic surfactants such as those sold under the trade names NEODOL ^™ , ALFOL ^™ , LIAL ^™ , LUTENSOL ^™ , etc. alcohol. Also known are alkyl ether sulfates such as alkyl polyethoxylated sulfates.

Another class of alkyl sulfate surfactants according to the present invention is one or more (preferably a mixture of two or more) mid-chain branched surfactants, preferably having the following chemical formula: Alkyl alkoxy alcohols:

Mid-chain branched alkyl sulfates having the formula:

and mid-chain branched alkylalkoxysulfates of the formula:

wherein the total number of carbon atoms in the branched primary alkyl portion of these formulas (containing R, R ¹ , and R ² branches, but not containing carbon atoms containing any EO/PO alkoxy moieties) is 14 to 20; and in addition to These surfactant mixtures wherein the average total number of carbon atoms in the branched primary alkyl portion of the formula above is in the range of greater than 14.5 to about 17.5 (preferably about 15 to about 17); R, R ¹ , and R ² each independently selected from hydrogen, C ₁ -C ₃ alkyl, and mixtures thereof, preferably methyl, as long as R, R ¹ , and R ² are not all hydrogen, and when z is 1, at least R or R ¹ Not hydrogen. M is a water soluble cation, and may contain more than one type of cation, eg a mixture of sodium and potassium. The index w is an integer of 0-13; x is an integer of 0-13; y is an integer of 0-13; z is an integer of at least 1; provided that w+x+y+z is 8-14. EO and PO represent ethyleneoxy units and propyleneoxy units, and their chemical formulas are respectively:

However, other alkoxy units especially 1,3-propyleneoxy, butoxy and mixtures thereof are suitable alkoxy units appended to the mid-chain branched alkyl moiety.

Preferred mid-chain branched surfactants are mixtures comprising surfactant systems. Thus when the surfactant system comprises alkoxylated surfactants, the index m represents the average degree of alkoxylation in the surfactant mixture. Such index m is at least about 0.01, preferably in the range of from about 0.1, more preferably from about 0.5, most preferably from about 1 to about 30, preferably to about 10, more preferably to about 5. When considering a mid-chain branched surfactant system comprising only alkoxylated surfactants, the value of the index m represents the distribution of the average degree of alkoxylation corresponding to m, or it may be a single m corresponds to the exact number of alkoxylated (eg ethoxylated and/or propoxylated) units of the particular chain.

Preferred mid-chain branched surfactants of the invention suitable for use in the surfactant system of the invention have the formula:

or the chemical formula is:

Wherein a, b, d, and e are integers, and a+b is 10-16, and d+e is 8-14; M is selected from sodium, potassium, magnesium, ammonium and substituted ammonium and mixtures thereof.

Surfactant systems of the present invention comprising mid-chain branched surfactants are preferably formulated in two embodiments. A first preferred embodiment encompasses mid-chain branched surfactants formed from feedstocks comprising 25% or less of mid-chain branched alkyl units. Thus, the mid-chain branched surfactant component will contain 25% or less of the surfactant molecules of the non-linear surfactant prior to incorporation with any other conventional surfactants.

A second preferred embodiment includes mid-chain branched surfactants formed from feedstocks comprising from about 25% to about 70% mid-chain branched alkyl units. Thus, the mid-chain branched surfactant component will contain from about 25% to about 70% of the surfactant molecules of the non-linear surfactant prior to incorporation with any other conventional surfactants.

U.S. Patent Application No. 60/061,971, Attorney Docket No. 6881P, October 14, 1997; U.S. Patent Application No. 60/061,975, Attorney Docket No. 6882P, October 14, 1997; U.S. Patent Application No. 60, October 14, 1997 /062,086, Attorney Docket No. 6883P; U.S. Patent Application No. 60/061,916, Oct. 14, 1997, Attorney Docket No. 6884P; U.S. Patent Application No. 60/061,970, Oct. 14, 1997, Attorney Docket No. 6885P; October 1997 These surfactants are further described in U.S. Patent Application No. 60/062,407 on the 14th, Attorney Docket No. 6886P: Other suitable mid-chain branched surfactants can be found in U.S. Patent Application Serial No. 60/032,035 (Docket No. 6401P), 60 /031,845 (Case No. 6402P), 60/031,916 (Case No. 6403P), 60/031,917 (Case No. 6404P), 60/031,761 (Case No. 6405P), 60/031,762 (Case No. 6409P). Mixtures of these branched chain surfactants and conventional linear surfactants are also suitable for use in the compositions of the present invention.

Among the anionic surfactants of the present invention which are not included in the alkyl sulfates according to the present invention, one class of anionic surfactants which may be used includes alkyl ester sulfonates. These are desirable because they can be prepared from renewable non-petroleum sources. The preparation of the alkyl ester sulfonate surfactant component can be accomplished according to known methods disclosed in the technical literature. For example, linear C8-C20 carboxylate esters can be sulfonated with _SO3 gas according to "Journal of the American Oleochemists'Society" vol. 52 (1975) pp. 323-329. Suitable starting materials include natural fatty materials such as derived from tallow, palm oil and coconut oil.

Preferred alkyl ester sulfonate surfactants, especially for laundry use, comprise alkyl ester sulfonate surfactants of the following structural formula:

Wherein R ³ is a C8-C20 hydrocarbon group, preferably an alkyl group or a mixture thereof; R ⁴ is a C1-C6 hydrocarbon group, preferably an alkyl group or a mixture thereof; and M is a soluble-salt-forming cation. Suitable salts include metal salts such as sodium, potassium, and lithium salts, and substituted or unsubstituted ammonium salts such as methyl-, dimethyl-, trimethyl-, and quaternary ammonium cations, such as tetramethyl-ammonium and dimethylpiperidinium salts, and cations derived from alkanolamines such as monoethanol-amine, diethanolamine, and triethanolamine. Preferably, R ³ is C10-C16 alkyl, and R ⁴ is methyl, ethyl or isopropyl. Especially preferred are methyl ester sulfonates in which R ³ is C14-C16 alkyl.

Another useful class of anionic surfactants includes alkylbenzene sulfonates. It includes hard (ABS, TPBS), linear types, also commonly known as LAS, and such as C ₉ -C ₂₀ linear alkylbenzene sulfonates, especially linear alkyl C ₁₀ -C ₁₅ sodium benzene sulfonates, which can be by known methods such as various HF or solid HF methods such as DETAL (UOP) method, or use other Lewis acid catalysts such as AlCl ₃ to prepare, or use acidic silica/alumina to prepare, or to prepare from chlorinated hydrocarbons. These surfactants are water-soluble salts or acids with a typical chemical formula of RASO ₃ M, wherein R is a branched or linear C10-C24 alkyl, preferably a C10-C20 alkyl, more preferably a C10-C18 alkyl; A is an aryl group, preferably benzene, or toluene, more preferably a benzene unit; and M is H or a cation, such as a metal cation (such as sodium, potassium, lithium, etc.), ammonium or substituted ammonium cations.

The surfactant system of the laundry detergent compositions of the present invention may also comprise from about 0.001%, preferably from about 1%, more preferably from about 5%, most preferably from about 10% to about 100%, preferably from about 60% by weight of the surfactant system , more preferably about 30% of one or more (preferably a mixture of two or more) modified alkylaryl sulfonate surfactants, or MLAS preferably surfactants wherein the aryl units are benzene ring, which has the chemical formula:

wherein L is an acyclic hydrocarbyl moiety containing 6 to 18 carbon atoms; R ¹ , R ² , and R ³ are each independently hydrogen or C ₁ -C ₃ alkyl, provided that R ¹ and R ² are not attached to L The end of the unit; M is a water-soluble cation with charge q, where a and b take values together to satisfy charge balance.

Co-pending U.S. Patent Application No. 60/053,319, Attorney Docket No. 6766P, filed July 21, 1997, and U.S. Patent Application No. 60/053,318, Attorney Docket No. 6767P, filed July 21, 1997, July 1997 U.S. Patent Application No. 60/053,321, Attorney Docket No. 6768P, filed July 21, 1997, U.S. Patent Application No. 60/053,209, Attorney Docket No. 6769P, filed July 21, 1997 60/053,328, Attorney Docket No. 6770P, U.S. Patent Application No. 60/053,186, filed July 21, 1997, Attorney Docket No. 6771P, U.S. Patent Application No. 60/105,017, filed October 20, 1998, Attorney Docket No. 7303P These and others are further described in U.S. Patent Application No. 60/104,962, Attorney Docket No. 7304P, filed October 20, 1998, and U.S. Patent Application No. 60/144,519, Attorney Docket No. 7663P, filed July 19, 1999 Suitable MLAS surfactants. Mixtures of these modified surfactants and conventional surfactants and/or branched chain surfactants as described herein are also suitable for use in the compositions of the present invention.

Examples of suitable anionic surfactants are given in "Surface Active Agents and Detergents" (Volume I and II, by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in US Patent 3,929,678, Laughlin et al., issued December 30, 1975 at Column 23, line 58 through Column 29, line 23.

The present compositions may also include other detersively useful anionic surfactants. This may include soap salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts), C8-C22 primary or secondary alkyl sulfonates, C8-C24 olefin sulfonates salts, sulfonated polycarboxylates prepared by sulfonation of alkaline earth metal citrate cleavage products as described in British Patent Specification 1,082,179, alkyl glycerol sulfonates, fatty acylglycerol sulfonates, fatty oleyl Glyceryl Sulfate, Alkylphenol Ethoxyether Sulfate, Paraffin Sulfonate, Alkyl Phosphate, Isethionate As Acyl Isethionate, N-Acyl Taurate, Methyl taurates, alkyl succinamidates and sulfosuccinates of fatty acid amides, sulfosuccinate monoesters (especially saturated and unsaturated C12-C18 monoesters), sulfosuccinates Acid diesters (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates, alkyl polysaccharide sulfates such as alkyl glucoside sulfates (non-ionic non-sulfate compounds will hereinafter described), branched primary alkyl sulfates, alkyl polyethoxy carboxylates having the chemical formula RO(CH ₂ CH ₂ O) _k CH ₂ COO ^- M ⁺ (wherein R is C8-C22 alkyl, k is an integer from 0 to 10, and M is a water-soluble salt-forming cation), and a fatty acid neutralized with isethionated and sodium hydroxide. Resin acids and hydrogenated resin acids are also suitable, such as those present in or derived from pine resin, hydrogenated turpentine, tall oil, or derived therefrom. Further examples are given in "Surface Active Agents and Detergents" (Volume I and II, by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in US Patent 3,929,678, Laughlin et al., issued December 30, 1975, at Column 23, line 58 through Column 29, line 23.

Another useful class of anionic surfactants are the so-called dianionic surfactants. These surfactants are those in which at least two anionic groups are present in the surfactant molecule. Co-pending U.S. Patent Serial Nos. 60/020,503 (Docket No. 6160P), 60/020,772 (Docket No. 6161P), 60/020,928 (Docket No. 6158P), 60/020,832 (Docket No. 6159P) and 60/020,773 (Docket No. 6162P), and U.S. Patents 60/023,539 (Docket No. 6192P), 60/023493 (Docket No. 6194P), 60/023,540 (Docket No. 6193P), filed August 8, 1996 Some suitable dianionic surfactants are further described in and 60/023,527 (Case No. 6195P), which are incorporated herein by reference.

C. Tablet products

Tablet detergent products of the present invention preferably contain, in addition to one or more hydrotropes ("binders" because of their binding effect in the tablet), one or more of the preferred ingredients hereinafter and optionally one or more conventional detergent additive materials. These conventional additive materials may comprise one or more of the solid particulate materials previously described in the section on liquid products and/or in the section on granular/powder products or below in the section on conventional detergent additive materials.

Detergent tablet formulations generally contain at least a small amount of binder in the composition to provide a cohesive effect and to promote tablet integrity. For the purposes of the present invention, the binding effect of the detergent matrix particulate material is characterized by the force required to break tablets extruded under controlled compression conditions based on the detergent matrix tested. A method for assessing tablet strength (and involving radial crushing pressure) is given in Pharmaceutical Dosage Forms: Tablets, Vol. 1, edited by H.A. Lieberman et al., 1989.

The incorporation of these hydrotrope compounds in the particulate material prepared according to the invention was found to have a binding effect when forming tablets by compression of the particulate material, while also providing excellent wash-water disintegration properties. The detergent tablet containing the hydrotrope has a higher tensile strength under a fixed pressure, or an equivalent tensile strength under a lower pressure, compared with a conventional tablet.

These hydrotropes, in addition to providing the cohesive effect, also provide the key ingredient in preventing gelation and/or thickening of the detergent compositions described herein. Gelation has previously been observed in detergent products prepared without the addition of a hydrotrope as defined in the present invention, when the product is first exposed to water and diluted with water. Without being bound by theory, it is believed that the gelation phenomenon is caused by the formation of a viscous surfactant phase (typically flakes) when surfactant-containing particles contact water at a defined surfactant concentration in a wash-liquor or wash-water. shape, globular or hexagonal phase). A correlation was found between the viscosity of the product-water mixture in the critical dilution range where gelation was observed and the amount of viscous surfactant phase formed in that range.

Without being bound by theory, it is believed that the aforementioned hydrotropes prevent the formation of sticky surfactant phases that can form upon dilution because the hydrotropes effectively interact with the ordered structured layer surfactant molecules, breaking them apart , promoting the formation of an isotropic low-viscosity surfactant phase.

The present invention also has the added benefit that the inclusion of these specific hydrotropes develops the "operating window" of the detergent tablet. When manufacturing detergent tablets on an industrial scale, operating limits relate to the range of bulk density of the detergent tablet. Because of a number of variables, the density of detergent tablets during commercial-scale manufacturing of detergent tablets varies somewhat from the ideal or preferred density. The operational limit is the density range around the preferred density where the tablet density is not exactly the preferred density, but is still desirable. Below the operating limit, the density is too low, the result of insufficient loading and cohesion during the compression step, and the tablet is very brittle and likely to break during handling and storage. Above the operating limit, the tablets are packed too tightly and the tablets may not dissolve and disperse adequately in the wash solution during the wash.

In addition to the above-mentioned hydrotropes, the detergent tablet may comprise additional non-gelling binders. Non-gelling adhesives not only provide binding but also aid in dissolution.

If non-gelling binders are used, suitable non-gelling binders include synthetic organic polymers such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates and water-soluble acrylate copolymers. The second edition of the Handbook of Pharmaceutical Excipients has the following binder categories: Gum Arabic, Alginic Acid, Carbopol, Sodium Carboxymethylcellulose, Dextrin, Ethylcellulose, Gelatin, Guar Gum, Hydrogenated I Type Vegetable Oil, Hydroxyethylcellulose, Hydroxypropylmethylcellulose, Liquid Glucose, Magnesium Aluminosilicate, Maltodextrin, Methylcellulose, Polymethacrylate, Povidone, Sodium Alginate, Starch and zein. Most preferred binders also have an active cleaning function in laundry washing, such as cationic polymers such as ethoxylated hexamethylenediamine quaternary ammonium compounds, bis(hexamethylene)triamines, or others such as Pentaamines, ethoxylated polyvinylamines, maleic acrylic polymers.

The non-gelling adhesive raw material is preferably a spray and therefore suitably has a melting point temperature below 90°C, preferably below 70°C, and even more preferably below 50°C, so as not to disperse the other active ingredients in the matrix. damaged or degraded. Most preferably non-aqueous liquid binders (ie not aqueous solutions) can be sprayed in molten form. However, they can also be solid binders, blended into the matrix by dry addition, but they have cohesive properties in tablets.

Detergent tablets prepared in accordance with the present invention will contain from about 0.05% to about 5%, preferably from about 0.1% to about 3%, most preferably from about 0.1% to about 1%, of a basic hydrotrope, wherein both Each polar group is separated from each other by at least 5, preferably 6 aliphatic carbon atoms. If non-gelling binder materials are optionally used, they will be used in the detergent tablet in an amount of about 0.1% to about 7%, preferably about 0.5% to about 5%, more preferably about 0.5% to about 5% of the detergent tablet. Preferably from about 1% to about 3% is present. If non-gelling binders are optionally used, they will be present in the detergent tablet in a ratio of non-gelling binder to characteristic hydrotropic binder of about 2:1 to about 60:1, preferably from about 3:1 to about 30:1, more preferably from about 3:1 to about 15:1.

Disintegrants - Although tablets must have good integrity prior to use, they must also disintegrate rapidly on contact with wash-water during use. It is known that disintegrants may be included to facilitate disintegration of tablets. Various classes of disintegrants are also known, including such disintegrants that cause disintegration by swelling of the disintegrant. Various swelling disintegrants have been proposed in the literature, the preferred directing mainly to starches, celluloses, and water-soluble organic polymers. Inorganic swelling disintegrants such as bentonite are also mentioned, for example in EP-A-466,484.

Some raw materials can act as binders and disintegrants. It is also mentioned in the literature that disintegrants may impart additional synergistic, anti-redeposition or fabric softening properties. The preferred disintegrating dose is 1-5%. EP-A-466,484 proposes that tablets may have a heterogeneous structure comprising a plurality of discrete regions, eg layers, inserts or coatings.

Tablet Manufacture - The detergent tablets of the present invention can be prepared simply by mixing the solid ingredients together and compressing the mixture in a conventional tablet press as used by the pharmaceutical industry. Preference is given to using the main ingredients, especially gelling surfactants, in particulate form. Any liquid ingredients, such as surfactants or suds suppressors, may be incorporated into the solid particulate ingredients in a conventional manner.

Ingredients such as builders and surfactants can be spray-dried in conventional manner and then compressed under suitable pressure. Tablets are preferably compressed according to the invention using a force of less than 100000N, more preferably less than 50000N, even more preferably less than 5000N and most preferably less than 3000N. Indeed the most preferred embodiment is to compress the tablet using a force of less than 2500N.

The particulate raw material used in the production of tablets according to the invention can be manufactured by any micronization or granulation method. An example of these processes is spray drying (in a co-current or counter-current spray drying tower), which generally gives low bulk densities of 600 g/l or below. Higher density particulate feedstocks can be granulated and compacted in a high shear batch mixer/granulator or by continuous granulation and compaction methods (e.g. using Lodige(R) CB and/or Lodige(R) KM mixer) to prepare. Other suitable methods include fluidized bed methods, powder extrusion (eg tumbling powder extrusion), extrusion, and any particulate material prepared by any chemical method such as flocculation, crystallization, and the like. Individual particles may also be any other particles, granules, spheres or granules.

The components of the particulate feedstock can be mixed together by any conventional means. Batch mixing is suitable eg in a concrete mixer, Nauta mixer, ribbon mixer or any other mixer. Alternatively, the mixing process can be carried out continuously by weighing the components onto a conveyor belt and mixing them in one or more tumblers or mixers. The non-gelling binder can be sprayed onto the mixture of some or all of the components of the particulate material. Other liquid ingredients can be sprayed onto the mixture of either separate or premixed components. For example perfume and optical brightener slurries can be sprayed. Finely divided glidants (separators such as zeolites, carbonates, silicas) can be added to the particulate material after spraying through the binder. It is preferable to make the mixture less sticky at the end of the treatment.

Tablets may be manufactured using any compression method, such as tabletting, briquette or extrusion, preferably tabletting. Suitable equipment includes standard single punches or rotary presses (eg Courtoy(R), Korch(R), Manesty(R), or Bonals(R)). Tablets prepared according to the invention preferably have a diameter of 20 mm to 60 mm, preferably at least 35 and up to 55 mm, and a weight of 15 g to 100 g. The ratio of tablet height to diameter (or width) is preferably greater than 1:3, more preferably greater than 1:2. The compaction pressure used to prepare these tablets is required to be no more than 100000kN/ ^m2 , preferably no more than 30000kN/ ^m2 , more preferably no more than 5000kN/ ^m2 , even more preferably no more than 3000kN/ ^m2 , and most preferably no more than 1000kN /m ² . In a preferred embodiment according to the invention, the tablet has a density of at least 0.9 g/cc, more preferably at least 1.0 g/cc, and preferably less than 2.0 g/cc, more preferably less than 1.5 g/cc, even more preferably Less than 1.25 g/cc and most preferably less than 1.1 g/cc.

Multi-layer tablets can be manufactured by known techniques.

Coating - The robustness of tablets according to the invention can be further improved by making coated tablets, the coating according to the invention covers non-coated tablets, thus further improving the tablet while maintaining or further improving dispersion mechanical properties.

In one embodiment of the invention, the tablet may then be spread such that the tablet does not absorb moisture, or only absorbs moisture at a very slow rate. The coating is also robust and thus moderates the mechanical shocks experienced by the tablet during handling, packaging and shipping, with no more than very low levels of breakage or abrasion. Finally it is preferred that the coating is brittle so that the tablet breaks when subjected to stronger mechanical shocks. It is also advantageous if the coating material can be dispersed under alkaline conditions or easily emulsified by surfactants. This has the advantage of avoiding the problem of visible residues in the window of a front loading washer during the wash cycle and avoids the deposition of particles or micelles of the coating material on the wash items.

Water solubility is determined following the test protocol of ASTM E1 148-87, entitled "Standard Test Method for Measurement of Solubility in Water".

Suitable coating materials are dicarboxylic acids. Particularly suitable dicarboxylic acids are selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecane Diacids, tridecanedioic acids and mixtures thereof. Preferably, the coating material has a melting point of 40°C to 200°C.

Coatings can be applied using a number of methods. Two preferred coating methods are: a) coating with molten feedstock; and b) coating with solution of feedstock.

In a), the coating material is applied at a temperature above its melting point and solidifies on the tablet. In b), the coating is applied from a solution and the solvent dries to leave an adherent coating. The substantially insoluble material can be applied to the tablet by, for example, spraying or dipping. Normally, when molten material is sprayed onto a tablet, it will quickly solidify to form a cohesive coating. When the tablet is dipped in the molten stock and then left, the rapid cooling again causes rapid solidification of the coating stock. It is clear that substantially insoluble starting materials with melting points below 40°C do not solidify sufficiently at room temperature, and it has also been found that starting materials with melting points above about 200°C cannot be practically used. The preferred melting range of the raw materials is 60°C to 160°C, more preferably 70°C to 120°C.

"Melting point" refers to the temperature at which a material becomes a clear liquid when heated slowly, eg, in a capillary tube.

Coatings of any desired thickness may be applied in accordance with the present invention. For most purposes, the coating is formed at 1% to 10%, preferably 1.5% to 5%, by weight of the tablet.

Preferably the tablet coating is very hard and provides additional strength to the tablet.

In a preferred embodiment of the invention, a disintegrant is added to the coating to improve the breakdown of the coating in the wash. Upon contact with water, the disintegrant will swell and break the coating into small pieces. This will improve the dispersion of the coating in the wash solution. The disintegrant is suspended in the coating melt in an amount of up to 30%, preferably 5% to 20%, most preferably 5 to 10% by weight. Possible disintegrants are described in Handbook of Pharmaceutical Excipients (1986). Suitable examples of disintegrants include starches: native, modified or pregelatinized starch, sodium starch gluconate; gums: agar gum, guar gum, carob gum, karaya gum, pectin, tragacanth Gum; croscarmylose sodium; polyvinylpolypyrrolidone; cellulose; carboxymethylcellulose; alginic acid and its salts including sodium alginate; siloxane; clay; polyvinylpyrrolidone; soybean polysaccharides; ion exchange resins and their mixture.

Tensile Strength - Depending on the composition of the starting material and the shape of the tablet, the pressure used can be adjusted so that it does not affect the tensile strength and splitting time in the washing machine. This method can be used to prepare uniform or layered tablets of any size or shape.

The tensile strength of cylindrical tablets corresponds to the radial crushing pressure (DFS), which is a way of expressing tablet strength and is determined by the following equation:

$<span\; class="notranslate">\; =</span>\frac{\mathrm{<span\; class="notranslate">\; 2</span>}\mathrm{<span\; class="notranslate">\; f</span>}}{\mathrm{<span\; class="notranslate">\; \&pi;Dt</span>}}$

Where F is the maximum force (in Newtons) that causes tensile failure (crushing), as determined by a VK200 Tablet Hardness Tester manufactured by Van Kell Industries Ltd. D is the tablet diameter and t is the tablet thickness.

(Method of Pharmaceutical Dosage Forms: Tablets Vol. 2, pp. 213-217) Preferably, the radial crushing pressure is at least 25 kPa.

This method can be similarly applied to non-cylindrical tablets, since the cross-section perpendicular to the height of the tablet is not circular, thus applying force in a direction perpendicular to the height of the tablet and normal to the sides of the tablet to determine tensile strength , where the tablet sides are perpendicular to the non-circular cross-section.

Optional conventional detergent additive ingredients

In addition to the components of the compositions of the present invention described above, the detergent compositions herein may preferably contain a wide variety of other additional ingredients.

(a) Inorganic Detergent Builders - The detergent compositions of the present invention may also optionally contain one or more inorganic detergent builders beyond the types listed above which also function as sources of alkalinity . These optional inorganic builders can include, for example, aluminosilicates such as zeolites. Aluminosilicate zeolites and their use as detergent builders are more fully discussed in US Patent 4,605,509, Corkill et al., issued August 12, 1986, which is incorporated herein by reference. Also suitable for use in the present detergent compositions are crystalline layered silicates such as those discussed in this '509 US Patent. If used, optional inorganic detergent builders can comprise from about 2% to about 15% by weight of the composition herein.

(b) Enzymes —for a wide variety of fabric washing purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains; prevention of bleed dye migration; and fabric restoration, formulations herein may Contains enzymes. It is believed that the addition of the above-mentioned characteristic hydrotropes will enhance the performance of enzymes in detergent compositions. This is because the hydrotrope increases the dissolution rate of the detergent composition, the rate at which the enzyme contacts water and becomes activated will also increase, and the corresponding detergency benefit provided by the activated enzyme will also increase. This behavior is seen in both aqueous and non-aqueous detergent compositions.

Added enzymes include proteases, amylases, lipases, mannanases, cellulases and peroxidases and mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as of vegetable, animal, bacterial, fungal and yeast origin. However, their choice depends on several factors such as pH-activity and/or stability optima, thermostability, stability relative to active detergents, builders, etc. Preference is given in this regard to bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases.

Enzyme is usually added in an amount sufficient to provide up to about 5 mg, more typically about 0.01 mg to about 3 mg of active enzyme per gram of composition. In other words, the present compositions will typically comprise from about 0.001% to about 5%, preferably from 0.01% to 1.0% by weight of a commercial enzyme preparation. Proteases are usually present in such commercial formulations in an amount sufficient to provide 0.005 to 0.1 Anson Units (AU) of activity per gram of composition.

。Novo Industries A/S的英国专利说明书1,243,784中叙述了这种酶和类似酶的制备。商业上有售的适宜于去除蛋白质-基污点的蛋白水解酶包括Novo Industries A/S(丹麦)出售的商品名为ALCALASE

和SAVINASE

(丹麦)、及International Bio-Synthetics公司(荷兰)出售的商品名为MAXATASE的蛋白水解酶。其他蛋白酶包括蛋白酶A(参阅1985年1月9日公布的欧洲专利申请130,756)和蛋白酶B(参阅1987年4月28日提出的欧洲专利申请系列号87303761.8和Bott等人1985年1月9日公布的欧洲专利申请130,756)。Suitable examples of proteases are subtilisins, which are obtained from special strains of Bacillus subtilis and Bacillus licheniformis. Another suitable protease obtained from a Bacillus strain with maximal activity throughout the pH range of 8-12 was developed and sold by Novo Industries A/S under the registered trade name ESPERASE

. The preparation of this and similar enzymes is described in British Patent Specification 1,243,784 to Novo Industries A/S. Commercially available proteolytic enzymes suitable for removing protein-based stains include those sold by Novo Industries A/S (Denmark) under the trade name ALCALASE

and SAVINASE

(Denmark), and International Bio-Synthetics (Netherlands) sold under the trade name MAXATASE of proteolytic enzymes. Other proteases include Protease A (see European Patent Application 130,756 published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8 filed April 28, 1987 and Bott et al. published January 9, 1985 European Patent Application 130,756).

、和NovoIndustries A/S的TERMAMYL

。Amylases include, for example, amylases described in British Patent Specification 1,296,839 (Novo Industries A/S), RAPDASE from International Bio-Syrithetics

, and TERMAMYL from NovoIndustries A/S

.

Mannanases include the following three mannan-degrading enzymes: EC 3.2.1.25: β-mannosidases, EC 3.2.1.78: Endo-1,4-β- Mannosidase, and EC 3.2.1.100: 1,4-β-mannobiosidase (IUPAC Classification - Enzyme Nomenclature, 1992 ISBN 0-12-227165-3, published by Academic Press).

More preferably, the detergent compositions of the invention comprise a beta-1,4-mannosidase (EC 3.2.1.78) known as mannanase. The term "mannanase" or "galactomannanase" means according to the literature the formal name mannan endo-1.4-β-mannosidase and the other name β-mannanase and endo- 1,4-Mannanase Defined as a mannanase that catalyzes the reaction that hydrolyzes any of mannan, galacto-mannan, gluco-mannan, and galacto-gluco-mannan 1,4-β-D-mannosidic linkage. In particular mannanases (EC 3.2.1.78) constitute a group of polysaccharases that degrade mannan and represent enzymes capable of cleaving polysaccharide chains containing mannose units, i.e. capable of cleaving mannan, grape-mannose Glycosidic linkages in glycans, galacto-mannan and galacto-gluco-mannan. Mannans are polysaccharides whose backbone consists of β-1,4-linked mannose; gluco-mannans are polysaccharides with more or less regularly alternating β-1,4-linked mannose and glucose backbones galacto-mannans and galacto-glucomannans are mannans and glucomannans with alpha-1,6 linked galactose side chains. These compounds may be acetylated.

和CELLUZYME

。Cellulase enzymes are used in instant detergent compositions, preferably in an amount sufficient to provide up to about 5 mg by weight, more preferably from about 0.01 mg to about 3 mg, of active enzyme per gram of composition. In other words, the present compositions preferably comprise from about 0.001% to about 5%, preferably from 0.01% to 1.0% by weight of a commercial enzyme preparation. Cellulases useful in the present invention include both bacterial or fungal cellulases. Preferably they have an optimum pH of 5 to 9.5. Suitable cellulases are disclosed by Barbesgoard et al. in U.S. Patent 4,435,307 issued March 6, 1984, which discloses fungal cellulase produced by Humicola insolens and Humicola strain DSM 1800, or produced by Sulfase 212 is a fungal cellulase produced by microorganisms belonging to the genus Aeromonas, and a cellulase extracted from the hepatopancreas of Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2.075.028, GB-A-2.095.275 and DE-OS-2.247.832. Additionally, particularly suitable cellulases for use herein are the cellulases disclosed in WO 92-13057 (Procter & Gamble). Most preferably, cellulase for use in instant detergent compositions is commercially available from NOVO Industries A/S under the product name CAREZYME

and CELLUZYME

.

，下文称作“Amano-P”。其他商业的脂肪酶包括AMANO-CES

，是源自粘色杆菌例如var.lipolyticum粘色杆菌NRRLB 3673的脂肪酶，商业上从日本Tagata的Toyo Jozo公司得到；此外还包括美国U.S.Biochemical公司和荷兰Disoynth公司的粘色杆菌脂肪酶，和源自唐菖蒲假单胞菌的脂肪酶。这里使用的优选的脂肪酶是商业上从Novo Industries A/S得到的由绒毛腐质霉衍生的LIPOLASE

酶(也参阅EPO 341,947)。Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group such as Pseudomonas stutzeri ATCC 19.154 as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application No. 53,20487, open to public examination on February 24,1978. This lipase can be obtained from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the trade name lipase P AMANO

, hereinafter referred to as "Amano-P". Other commercial lipases include AMANO-CES

, is a lipase derived from Chromobacterium vixosa such as var. Lipase from Pseudomonas gladioli. A preferred lipase for use herein is LIPOLASE derived from Humicola tomentosa commercially available from Novo Industries A/S

Enzymes (see also EPO 341,947).

Peroxidase enzymes are used in combination with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used for "solution bleaching", ie preventing dyes or colorants removed from a substrate from migrating to other substrates in the wash solution during the wash run. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromoperoxidase. Detergent compositions containing peroxidases are disclosed, for example, in PCT International Application WO 89/099813 by O. Kirk, published October 19, 1989 and assigned to Novo Industries A/S.

A wide range of enzyme materials and methods of incorporating them into synthetic detergent compositions are also disclosed in US Patent 3,553,139, issued January 5, 1971 to McCarty et al. These enzymes are further disclosed in US Patent 4,101,457, issued July 18, 1978 to Place et al., and US Patent 4,507,219, issued March 26, 1985 to Hughes. Enzyme materials useful in liquid detergent formulations and their incorporation into such formulations are disclosed in US Patent 4,261,868, Hora et al., issued April 14, 1981. A variety of techniques can be used to stabilize enzymes for use in detergents. Enzyme stabilization techniques are disclosed and demonstrated in U.S. Patent 3,600,319, published August 17, 1971 by Gedge et al., and in European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, by Venegas. Enzyme stabilization systems are also described, for example, in US Patent No. 3,519,570. It is especially preferred herein to use enzymes which are added to the compositions herein in the form of conventional granulated enzymes. These particles will generally range in size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns, and will be suspended throughout the liquid phase of the composition. Enzyme granules in the compositions of the invention were found to exhibit particularly favorable enzyme stability in terms of retention of enzyme activity over time compared to other enzyme forms. Thus, compositions using enzyme granules need not contain conventional enzyme stabilizers, which must often be used when enzymes are incorporated into aqueous liquid detergents.

(c) Chelating Agents - The present detergent compositions may also optionally contain chelating agents which are used in the present detergent compositions to chelate metal ions such as iron and/or manganese. Such chelating agents are thus suitable to form complexes with metal impurities in the composition which would otherwise tend to reduce the activity of composition components such as peroxygen bleach. Useful chelating agents may include aminocarboxylates, phosphonates, aminophosphonates, polyfunctional-substituted aromatic chelating agents, and mixtures thereof.

Amino carboxylates used as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethyl-ethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate , triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, ethylenediamine disuccinate, and ethanol diglycine. Alkali metal salts of these starting materials are preferred.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention if at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylene-phosphonium salts) such as DEQUEST. Preferred These amino phosphonates do not contain alkyl or alkenyl groups of more than about 6 carbon atoms.

Preferred chelating agents include hydroxy-ethyldiphosphonic acid (HEDP), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminedisuccinic acid (EDDS) and dipicolinic acid (DPA) and their salts. Of course, the chelating agent can also function as a detergent builder in the washing/bleaching of fabrics using the present compositions. If used, chelating agents may comprise from about 0.1% to about 4% by weight of the composition. More preferably chelating agents will comprise from about 0.2% to 2% by weight of the detergent compositions herein.

(d) Suds suppressors - Because of the high concentration in detergent compositions, suds suppressors are of particular importance in the present invention. The use of suds suppressors in "high concentration cleaning processes" is described in great detail in US Patent Nos. 4,489,455 and 4,489,574.

A wide variety of materials are used as suds suppressors. Suds suppressors are well understood by those skilled in the art. See, for example, Kirk Othmer's Encyclopedia of Chemical Engineering, Third Edition, Vol. 7, pages 430-447 (published by John Wiley & Sons, 1979). A particularly important class of suds suppressors includes monocarboxylic fatty acids and their soluble salts. See US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. Monocarboxylic fatty acids and salts thereof useful as suds suppressors typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium, and lithium salts and ammonium and alkanolammonium salts.

The present detergent compositions may also contain non-surfactant suds suppressors including, for example, high molecular weight hydrocarbons, N-alkylated aminotriazines, monostearyl phosphate, silicone suds suppressors, secondary alcohols (for example, 2-alkyl alkanols) and mixtures of these alcohols with silicone oils. Hydrocarbon suds suppressors are described, for example, in US Patent 4,265,779, Gandolfo et al., issued May 5,1981. Silicone suds suppressors are well known in the art, for example, in U.S. Patent 4,265,779, Gandolfo et al., published May 5, 1981, and European Patent Application 89307851.9, Starch, M.S., published February 7, 1990 public. Mixtures of alcohols and silicone oils are described in US Patents 4,798,679, 4,075,118 and EP 150,872.

Additional examples of the aforementioned suds suppressors can be found in Pramod K. Reddy's provisional patent application, filed November 6, 1998, entitled "Hydrophilic Index of Aqueous Liquid Laundry Detergent Compositions Containing LAS", on file In Patent Collaboration, P&G Docket No. 7332P, Serial No. 60/107,477, the contents of which are incorporated herein by reference.

Preferred particulate foam control agents for use herein comprise a silicone antifoam compound, an organic material and a support material, wherein the silicone antifoam compound and the organic material are deposited on the support material. The carrier material is preferably indigenous starch or zeolites. The silicone antifoam compound is selected from polydiorganosiloxanes, solid silica, and mixtures thereof. Preferred organic raw materials are selected from:

(a) at least one fatty acid having a carbon chain of 12 to 20 carbon atoms, said organic material having a melting point in the range of 45°C to 80°C and being insoluble in water:

(b) at least one aliphatic alcohol having a carbon chain of 12 to 20 carbon atoms, said organic material having a melting point in the range of 45°C to 80°C and being insoluble in water;

(c) a mixture of at least one fatty acid and one fatty alcohol, each having a carbon chain containing 12 to 20 carbon atoms, said organic material having a melting point in the range of 45°C to 80°C and being insoluble in water;

(d) Organic raw materials containing glycerol fatty acid monoesters having a carbon chain of 12 to 20 carbon atoms with a melting point in the range of 50°C to 85°C; and

(e) dispersion polymers; and mixtures thereof.

Preferably the dispersing polymer is selected from copolymers of acrylic acid and maleic acid, polyacrylates and mixtures thereof.

Useful silicone suds suppressors known in the art are disclosed, for example, in U.S. Patent 4,265,779, Gandolfo et al., published May 5, 1981, and in European Patent Application 89307851.9, Starch, M.S., published February 7, 1990. antifoam agent. Silicone antifoam and foam control agents in granular detergent compositions are disclosed in US Patent 3,933,672 to Bartolotta et al. and US Patent 4,652,392 to Baginski et al., issued March 24, 1987. An example of a silicone based suds suppressor as used herein is the degree of suds suppression of a micronized foam control agent, the basic composition of which is:

(a) a polydimethylsiloxane fluid having a fluid viscosity of from about 20 cs to about 1,500 cs at 25°C;

(b) About 5 to about 50 parts of SiO ₂ units _, SiO _{2 units} and (CH ₃ ) _{3 SiO 1/2 2} in a ratio of 0.6:1 to about 1.2:1; and

(c) From about 1 to about 20 parts by weight of solid silica gel per 100 parts by weight of (i).

Additional suds suppressors suitable for use in the present invention are described in greater detail in US Patent 5,762,647, Brown et al., issued June 9,1998.

(e) Dye Transfer Inhibiting and Other Fabric Care Components -The compositions of the present invention may also include one or more materials which are effective to inhibit the transfer of dyes from one fabric to another during the cleaning process. These agents may be included either in the liquid phase containing the non-aqueous surfactant or in the solid particulate feedstock.

Typically such dye transfer inhibitors include polyvinylpyrrolidone polymers, N-polyamine oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof . These agents are typically included in amounts of from about 0.01% to about 10%, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%, by weight of the composition.

More specifically, the preferred polyamine N oxide polymers for use herein contain units of the following structural formula: R-Ax-P, where P is a polymerizable unit to which an N-O group may be attached, or the N-O group may be Form part of a polymerizable unit, or N-O groups can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O- , -N=; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof, which may have an N-O group attached The nitrogen of the group, or the N-O group is part of these groups. Preferred N-oxide polyamines are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

The N-O group can be represented by the following structural formula:

wherein R ₁ , R ₂ , R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the NO group may be attached to the above group on or form part of any of the aforementioned groups. The amine oxide units of the polyamine N-oxides have a pKa<10, preferably pKa<7, more preferably pKa<6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones are polyethylenes, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. Amine N-oxide polymers typically have a ratio of amine to amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or appropriate degree of N-oxidation. Polyamine oxides are available in virtually any degree of polymerization. The average molecular weight is typically in the range of 500 to 1,000,000, more preferably 1,000 to 500,000, most preferably 5,000 to 100,000.

The most preferred polyamine N-oxide useful in the present detergent compositions is poly(4-vinyl-pyridine N-oxide) having an average molecular weight of about 50,000 and a ratio of amine to amine N-oxide of about 1:4 . This class of preferred feedstocks is known as "PVNO".

Further suitable dye transfer inhibitors can be found in US Patent 5,466,802, Panandiker et al., issued November 14, 1995, the disclosure of which is incorporated herein by reference.

In addition to dye transfer inhibitors, the present invention further encompasses additional agents that provide fabric care functionality. As noted above, the addition of these agents may be necessary because the high concentration of detergent in the aqueous wash solution used in the present invention may damage garments and fabrics that come into contact with the aqueous wash solution.

Thus the present invention may also include materials which, when added to laundry detergent products, bind themselves to the fibers of fabrics and textiles washed with the product, thereby reducing or minimize. Of course, any such additional materials for detergent products should be able to benefit the appearance and integrity of the fabrics without unduly interfering with the laundry detergent product's ability to perform its intended function. Such fabric appearance benefits include, for example, improved overall appearance of laundered fabrics, reduced pill and fuzz formation, color protection from fading, improved abrasion resistance, and the like.

One such fabric conditioner is Polyethyleneimine 30, PEI 600 E20, which acts specifically to prevent dye migration from the surface of the garment into aqueous wash solutions, but also provides other fabric care benefits, which has the general chemical formula:

where B is the extension of the polyethyleneimine backbone through branches. E is an ethyleneoxy unit having the formula:

-(CH ₂ CH ₂ O) _m H

where the average value of m is about 20. Here an average value of 20 means that sufficient ethylene oxide or other suitable reactant is reacted with the polyethyleneimine starting material to fully ethoxylate each N-H unit to 20 ethoxy groups. However, those skilled in the art recognize that the hydrogen atoms of some N-H units will be replaced by less than 20 ethoxy units and some will be replaced by more than 20 ethoxy units, so that the average number of ethoxylations is 20.

The units making up the polyalkyleneimine backbone are primary, secondary and tertiary amine units. A primary amine unit has the following chemical formula:

H ₂ N-CH ₂ CH ₂ ]- and -NH ₂

It is the terminal group that terminates the main chain and any branches; the secondary amine unit has the following chemical formula:

Its hydrogen atoms are replaced by an average of 20 ethyleneoxy units after modification; and the tertiary amine unit has the following chemical formula:

It is the branch point of the main chain and the secondary chain, and B represents the extension of the chain structure through the branch. Tertiary amine units have no substitutable hydrogen atoms and therefore cannot be modified by substitution with ethyleneoxy units. Cyclization may occur during the formation of the polyamine backbone, and therefore some amount of cyclic polyamine may be present in the original polyalkyleneimine backbone mixture. In the same way as linear and branched polyalkyleneimines, each primary and secondary amine unit of the cyclic alkyleneimines is modified by the addition of alkyleneoxy units.

The indices w, x and y have values such that the polyethyleneimine backbone has an average molecular weight of about 600 Daltons before modification. In addition, those skilled in the art recognize that each branch must be terminated with a primary amine unit, thus the value of the index w is y+1 when no cyclic amine backbone is present. _The average molecular weight of each ethylene backbone _-NCH2CH2- unit is about 43 Daltons.

The polyamines of the invention can be prepared, for example, by the polymerization of ethyleneimine in the presence of catalysts such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid and the like. US Patent 2,182,306 issued December 5, 1939 by Ulrich et al., US Patent 3,033,746 issued May 8, 1962 by Mayle et al., US Patent 2,208,095 issued July 16, 1940 by Esselmann et al. Specific methods of preparing these polyamine backbones are disclosed in US Patent 2,806,839, issued September 17, 1957, and US Patent 2,553,696, issued May 21, 1951 to Wilson, the entire contents of which are incorporated herein by reference.

Other suitable fabric care agents for use in the present detergent compositions include dye maintenance polymers. An example of such a polymer is the imidazole-epichlorohydrin adduct:

(idealized structure)

It has an imidazole:epichlorohydrin ratio of 1.36:1. Further dye maintenance polymers and tests of dye maintenance parameters are described in the co-pending provisional application entitled "Laundry Detergent Compositions with Cationic Charged Dye Maintenance Polymers" by Rajan K. Panandiker et al., 1999 Filed March 25, 2009, with P&G Docket No. 7488P and Serial No. 60/126,074, the contents of which are incorporated herein by reference. As noted above, these dye maintenance polymers provide overall fabric care functionality in addition to color care protection.

(f) Thickeners, Viscosity Control Agents and/or Dispersants -The detergent compositions herein may also optionally contain polymeric materials to enhance the ability of the compositions to maintain their solid particulate components in suspension. Such materials may thus function as thickeners, viscosity control agents and/or dispersants. This material is often a polymeric polycarboxylate, but may include other polymeric materials such as polyvinylpyrrolidone (PVP) or polyamide resins.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably the carboxylic acid form monomers. Unsaturated monomeric carboxylic acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, methyl fumaric acid, acid and methylenemalonic acid. The presence of carboxyl-free monomer segments such as vinylmethyl ether, styrene, ethylene, etc. in these polymeric polycarboxylates is suitably provided that such segments do not constitute more than about 40% by weight of the polymer.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers useful herein are water-soluble salts of polyacrylic acid. The average molecular weight of such acid type polymers is preferably in the range of about 2,000-100,000, more preferably about 2,000-10,000, even more preferably about 4,000-7,000, and most preferably about 4,000-5,000. Such water-soluble salts of acrylic acid polymers may include, for example, alkali metal salts. Soluble polymer materials of this type are known. For example, US Patent 3,308,067, Diehl, issued March 7, 1967, discloses the use of polyacrylates of this type in detergent compositions. This material can also perform the function of a builder.

Other suitable polymeric materials suitable for use as thickeners, viscosity control agents and/or dispersants include: polymers of castor oil derivatives, polyurethane derivatives, and polyethylene glycol.

If used, optional thickeners, viscosity control agents and/or dispersants are present in the present compositions at a level of from about 0.1% to 4% by weight. More preferably, such materials will comprise from about 0.1% to about 2% by weight of the detergent compositions herein.

(g) Clay Soil Removal/Anti-Redeposition Agents - The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. If used, soil release materials herein can comprise from about 0.01% to about 5% by weight of the compositions.

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are further described in US Patent 4,597,898, VanderMeer, issued July 1,1986. Another group of preferred clay soil remover-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27,1984. Other clay soil removal/anti-redeposition agents that can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; Zwitterionic polymers disclosed in published European Patent Application 112,592 to Gosselink; and amine oxides disclosed in US Patent 4,548,744 to Connor, issued October 22,1985. Preferred clay soil removal compounds include ethoxylated quaternized amines. Preferred ethoxylated quaternized amine materials are selected from compounds having the following general chemical formula:

wherein each x is independently less than about 16, preferably from about 6 to about 13, more preferably from about 6 to about 8, or wherein each x is independently greater than about 35. Those starting materials as defined above which are suitable for use in the present invention are commercially available from the German companies BASF and Witco Chemicals.

It has been determined that the degree of ethoxylation is important to the viscosity of the final detergent compositions described herein. Especially for the following general structural formula:

When x is less than about 13, the ethoxylated quaternized amine clay soil removal material can be added as a liquid to the liquid heavy duty detergent compositions of the present invention without causing adverse effects at low temperatures. Welcome thickening. Also, when the structure is the same but the degree of ethoxylation is greater than about 35, i.e., when x is greater than about 35, these higher ethoxylated materials can be added to the formulation as stable solids that do not melt at elevated temperatures, And does not cause thickening of the product at low temperature.

It will of course be understood that other conventional optical brightener type compounds may optionally be used in the present compositions to provide conventional fabric "brightness" benefits rather than true dye transfer inhibiting benefits. This application to detergent formulations is routine and well understood.

Other clay soil removal and/or anti-redeposition agents known in the art may also be used in the present compositions. Another preferred class of anti-redeposition agents includes carboxymethylcellulose (CMC) materials. These materials are well understood in the art.

(h) Liquid Bleach Aids - The detergent compositions herein may optionally contain bleach aids which are liquid at room temperature which are added in liquid form to the liquid phase of the detergent compositions herein. One such liquid bleach builder is triacetin, which acts as a solvent during storage of the composition, but upon release into the wash solution is peroxidized to function as a bleach builder. Other examples of bleach aids include acetyl triethyl citrate (ATC) and nonanoyl valerolactam. Liquid bleach aids are soluble in the liquid phase of the present compositions.

(i) Brighteners, Dyes and/or Perfumes - The detergent compositions herein may also optionally contain conventional brighteners, bleach catalysts, dyes and/or perfumes. Of course these brighteners, silicone oils, bleach catalysts, dyes and perfumes must be compatible and non-reactive with the other composition components in aqueous or non-aqueous liquid environments. If present, brighteners, dyes and/or fragrances herein will typically comprise from about 0.0001% to 2% by weight of the composition.

(j) Structural Elasticity Agents - The liquid detergent compositions of the present invention may also contain from about 0.1% to 5%, preferably from about 0.1% to 2% by weight, of finely divided solid particulate materials which may include silica such as fumed di Silica, titanium dioxide, insoluble carbonates, finely divided carbon, SD-3 organobentonite, clay, or mixtures of these materials. Clays are well known to those skilled in the art and are commercially available as products from Rheox Corporation. Such finely particulate materials function as structural elastic agents in the products of the present invention. These materials have an average particle size in the range of about 7 to 40 nanometers, more preferably about 7 to 15 nanometers. These materials have specific surface areas in the range of about 40 to 400 m ² /g.

The finely divided elastomeric agent material herein improves the shipping stability of liquid detergent products by increasing the elasticity of the surfactant-structured liquid phase without increasing product viscosity. This makes the product resistant to the high frequency vibrations that may be encountered during transportation, so that it does not experience undesired structural damage that would cause the product to settle.

When titanium dioxide is used, this material also imparts a clean white color to the aerosol material in the detergent compositions, an effect which improves the overall appearance of the product.

(k) Microspheres - Microspheres can be used in the present invention. Suitable microspheres may be formed from one or more water-insoluble materials selected from the group consisting of polymers, silicon-containing materials, ceramic materials, and mixtures thereof. For a further discussion of microspheres, see the Kirk-Othmer Encyclopedia of Chemical Engineering, Third Edition, Volume 16, pages 628-651 "Microencapsulation" (John Wiley & Sons, 1979), the contents of which are incorporated herein by reference.

The polymeric microspheres of the present invention are preferably made from water-insoluble materials selected from the group consisting of thermoplastics, acrylonitrile, methacrylonitrile, polyacrylonitrile, polymethacrylonitrile, and mixtures thereof. The silicon-containing microspheres of the present invention are preferably made from one or more silicon-containing raw materials selected from glasses. Particular preference is given to borosilicate glass.

、LUXSIL

、Q-CEL、SPHERICEL

；和Malinckrodt公司商标为ALBUMEX

的产品。Commercially available microspheres are available under the trade name EXPANCEL from Akzo-Nobel, Sweden. ;PQ's product names are PM6545, PM6550, PM7220, PM7228, EXTENDOSPHERES

、LUXSIL

、Q-CEL 、SPHERICEL

; and the Malinckrodt Corporation trademark is ALBUMEX

The product.

Examples of suitable microspheres and liquid detergents containing microspheres can be found in co-pending provisional patent application by Broeckx et al., entitled "Stable Non-Aqueous Liquid Laundry Detergent Comprising Low Density Particles" Agents," with P&G Case No. 7417P, Provisional Serial No. 60/119,555, filed February 10, 1999, the contents of which are incorporated herein by reference.

In addition to the types of microspheres described above, suitable microspheres for use in the present invention may also be made from wash-water soluble biological materials such as starches and proteins, as described in great detail in co-pending provisional patent application by Sadlowski et al. , titled "Non-Aqueous Liquid Detergents and Wash-Water Soluble Low-Density Filler Particles," P&G Case No. 7707P, filed August 10, 1999, the contents of which are incorporated herein by reference.

In addition, the microspheres used in the present invention can serve as the center of particles formed by substantially enclosing the detergent components in the center layer. The list of these ingredients includes non-exclusively organic and inorganic builder materials, alkali source materials and other coating components. Coated microspheres are described in detail in a co-pending provisional patent application by Aouad et al., entitled "Non-Aqueous Liquid Detergents with Low Density Filler Particles Soluble in Wash-Water", P&G Case No. 7708P, filed August 10, 1999, the contents of which are incorporated herein by reference. Coated microspheres are also discussed in co-pending provisional application P&G Docket No. 7707 of Sadlowski et al., incorporated above.

(i) Effervescent Agent - In another preferred embodiment of the invention the tablet further comprises an effervescent agent.

Effervescence is here defined as the chemical reaction between a source of soluble acid and an alkali metal carbonate to form carbon dioxide gas, resulting in the evolution of gas bubbles from the liquid, i.e.:

C ₆ H ₈ O ₇ +3NaHCO ₃ →Na ₃ C ₆ H ₅ O ₇ +3CO ₂ +3H ₂ O

Further examples of acid and carbonate sources and other effervescent systems can be found in (Pharmaceutical Dosage Forms: Tablets Vol. 1 pp. 287-291).

Effervescent agents may be added to the tablet mixture in addition to the detergent ingredients. The addition of effervescent agents to detergent tablets improves the break-up time of the tablets. Preferably the amount of effervescent agent is 5-20% by weight of the tablet, and most preferably 10-20%. Preferably the effervescent agent is added as agglomerates or compacts of different particles and not as spacer particles.

Due to the gas caused by tablet effervescence, a tablet can have a higher D.F.S. and still have the same disintegration time as a non-effervescent tablet. When the effervescent tablet maintains the same D.F.S as the non-effervescent tablet, the splitting time of the effervescent tablet will be faster.

Further co-dispersants can be provided by using compounds such as sodium acetate or urea. A list of suitable dispersants can also be found in Pharmaceutical Dosage Forms: Tablets Vol. 1 2nd Edition, edited by H.A. Lieberman et al. ISBN 0-8247-8044-2.

The effervescent system may comprise acids and bases such as citric acid and sodium bicarbonate; and/or the effervescent system may comprise enzymes such as catalase and/or peroxidase and a source of peroxide such as hydrogen peroxide .

(m) Binders - Non-gelling binders may be incorporated into the tablet-forming granules to further aid in dispersion.

If non-gelling binders are used, suitable non-gelling binders include synthetic organic polymers such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates and water-soluble acrylate copolymers. The second edition of the Handbook of Pharmaceutical Excipients has the following binder classes: Gum Arabic, Alginic Acid, Carbopol, Sodium Carboxymethylcellulose, Dextrin, Ethylcellulose, Gelatin, Guar Gum, Type I Hydrogenated vegetable oil, hydroxyethylcellulose, hydroxypropylmethylcellulose, liquid dextrose, magnesium aluminosilicate, maltodextrin, methylcellulose, polymethacrylate, povidone, sodium alginate, starch and corn gluten. The most preferred binders also have an active cleaning function in laundry, such as cationic polymers i.e. ethoxylated hexamethylenediamine quaternary ammonium compounds, bis(hexamethylene)triamine or others such as pentamine, ethoxylated Hydroxylated polyvinylamines, maleic acrylic polymers.

The non-gelling adhesive raw material is preferably a spray and therefore suitably has a melting point temperature below 90°C, preferably below 70°C, and even more preferably below 50°C, so as not to disperse the other active ingredients in the matrix. damaged or degraded. Most preferably non-aqueous liquid binders (ie not aqueous solutions) can be sprayed in molten form. However, they can also be solid binders, blended into the matrix by dry addition, but they have cohesive properties in tablets.

Preferably the non-gelling binder material is used in an amount of 0.1 to 15% of the composition, more preferably below 5%, and especially below 2% by weight of the tablet if the binder is a non-laundry active material .

The use of gelling binders in liquid or molten form, such as nonionic surfactants, is preferably avoided. Nonionic surfactants and other gelling binders are not excluded from the composition, but are preferably processed into detergent tablets as particulate raw components rather than liquids.

(n) Clay - Clay minerals used in instant compositions to provide softening properties can be described as three-layer expandable clays, namely alumino-silicate and magnesium silicate salts, having an ion exchange rate of at least 50 meq/100 g clay capacity. The term "expandable" used to describe clay relates to the ability of layered clay structures to swell or expand upon exposure to water. The three-layer expandable clays used here are those materials geologically classified as smectites.

There are two distinct classes of smectite-type clays: the first class of smectites has alumina present in a silicate crystal lattice; the second class of smectites has magnesium oxide present in a silicate crystal lattice. The general chemical formulas of alumina and magnesia smectite clays are Al ₂ (Si ₂ O ₅ ) ₂ (OH) ₂ and Mg ₃ (Si ₂ O ₅ )(OH) ₂ , respectively. It should be recognized that the range of water of hydration in the above formula will vary depending on the treatment the clay is subjected to. This is not critical for the use of smectite clays in the present invention, the expandable properties of the hydrated clays are determined by the silicate lattice structure. In addition, in the lattice of smectite crystals, atoms can be replaced by iron and magnesium, and metal cations such as Na ⁺ , Ca ⁺⁺ and H ⁺ coexist in the water of hydration to provide charge balance. Unless noted below, such cationic substitutions are immaterial to the clay's use herein since the desired physical properties of the clay are not substantially altered thereby.

The three-layer expandable alumino-silicates useful herein are further characterized by a dioctahedral crystal lattice, whereas the expandable three-layer magnesium silicates have a trioctahedral crystal lattice.

As noted above, the clays used in the compositions of the present invention contain cationic counterions, such as hydrogen, sodium, potassium, calcium, magnesium, and the like. It is customary to identify clays on the basis of one predominant or only absorbed cation, eg a sodium clay is a clay in which the absorbed cation is predominantly sodium. Such absorbed cations are able to participate in exchange reactions with cations present in the aqueous solution. A typical exchange reaction involving smectite-type clays is represented by the following equation:

Smectite clay (Na)+NH ₄ OH→Smectite clay (NH ₄ )+NaOH.

Because one equivalent of ammonium ion replaces one equivalent of sodium in the above equilibrium reaction, it is customary to measure the cation exchange capacity (sometimes referred to as "basic exchange capacity") in terms of milliequivalents exchanged per 100 g of clay (meq./100 g). The cation exchange capacity of clays can be determined by a variety of methods including electrodialysis, exchange with ammonium ions followed by titration or the methylene blue method in Grimshaw, "The Chemistry and Physics of Clays", Interscience Publishing (1971) 264-265 page fully sets out all these methods. The cation exchange capacity of clay minerals involves factors such as the expandable nature of the clay, the charge of the clay determined at least in part by the lattice structure, and the like. The ion exchange capacities of clays vary over a wide range, from about 2 meq/100 g for kaolin to about 150 meq/100 g or greater for certain smectite clays. Illite clays have ion exchange capacities in the somewhat lower range, ie illite clays average about 26 meq/100g.

Illite and kaolinite clays, due to their relatively low ion exchange capacity, are not preferred clays for use in instant compositions. As noted above, illite and kaolinite clays are indeed the major constituents of clay soils which are removed from fabric surfaces by the present compositions. However, smectites such as nontronite, which has an ion exchange capacity of about 70 meq/100g, and montmorillonite, which has an ion exchange capacity greater than 70 meq/100g, have been found useful in instant compositions which deposit on fabrics to provide the desired softening effect. Thus, clay minerals useful herein are characterized as expandable three-layer smectite-type clays having an ion exchange capacity of at least about 50 meq/100 g.

While not intending to be bound by theory, it appears that the advantageous softening (and potentially dye scavenging, etc.) functionality of the instant composition is due to the physical and ion exchange properties of the clay used. This illustrates that experiments have shown that non-scalable clays, such as kaolin and illite clays, two classes of which have ion exchange capacities below 50 meq/100 g, do not provide the favorable characteristics of clays used in instant compositions.

The smectite clay used in this composition was all commercially available. These clays include, for example, montmorillonite, nontronite, nontronite, hectorite, saponite, sauconite, and vermiculite. Here clay is available in a variety of commercial products such as Thixogel #1 and Gelwhite GP from Georgia Kaolin Company, Elizabeth, NJ; Volclay BC and Volclay #325 from American Colloid Company, Skokie, Illinois; Company's Black Mountain Bentonite BH450; and Veegum Pro and Veegum F from R.T. Vanderbilt Company. It should be recognized that the smectite-type minerals available under the above trade names may comprise loose mixtures of various mineral entities. This mixture of smectite minerals is suitable for use here.

When using any of the smectite-type clays useful herein with a cation exchange capacity of at least about 50 meq/100 g, certain types of clays are preferred. For example Gelwhite GP is a very white form of smectite clay so it is preferred when formulating white granular detergent compositions. The smectite-type clay mineral Volclay BC contains at least 3% iron (expressed as _Fe2O3 ) in its crystalline lattice, has _a very high ion exchange capacity and is the most effective and practical clay for laundry compositions One, it is preferable from the standpoint of product performance.

的x-射线衍射模式的常识优点来选择。这个特征模式和上述方式进行的交换容量测定的结合，为这里公开的粒状洗涤剂组合物中特殊绿土-型矿物的应用提供了选择的基础。Clay minerals suitable for use here can be shown precisely by smectite14

The X-ray diffraction pattern is selected on the basis of common sense advantages. The combination of this characteristic model and the exchange capacity measurements performed in the manner described above provides a basis for selection for the use of particular smectite-type minerals in the granular detergent compositions disclosed herein.

The clay is preferably predominantly in granular form, at least 50% (preferably at least 75% or at least 90%) in granular form, with a particle size of at least 100 mm and up to 1800 mm, preferably up to 1180 mm, preferably 150 to 850 mm. Preferably the amount of clay in the granule is at least 50%, usually at least 70% or 90% by weight of the granule.

(o) Flocculants - Most polymers that flocculate clay are relatively long chain polymers and copolymers derived from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol , vinylpyrrolidone and ethyleneimine. Also suitable are gums such as guar gum.

Polymers of ethylene oxide, acrylamide or acrylic acid are preferred. If the molecular weight of these polymers is in the range of 100,000 to 10 million, the deposition of the fabric softening clay is significantly enhanced. Preferably these polymers have a weight average molecular weight of 150,000 to 5 million.

The most preferred polymer is poly(ethylene oxide). The molecular weight distribution is readily determined using gel permeation chromatography with reference to a standard poly(ethylene oxide) having a narrow molecular weight distribution.

Preferably the amount of flocculant is 0.5-10% by weight of the tablet, most preferably about 2-6%.

Preferably the flocculant is predominantly in particulate form, at least 50% by weight (preferably at least 75% and most preferably at least 90%) is in particulate form, having a particle size of at least 100 mm up to 1800 mm, preferably up to 1180 mm and most preferably from 150 to 850 mm, Preferably the amount of flocculant in the granule is at least 50%, usually at least 70% or 90% by weight of the granule.

Other ingredients typically used in detergent compositions and which may be incorporated into detergent tablets of the present invention include chelating agents, soil release agents, anti-soil redeposition agents, dispersants, brighteners, suds suppressors, fabric softeners agents, dye transfer inhibitors and fragrances.

It should be noted that improved disintegration or dispersion can be achieved if the clay material is compressed prior to incorporation into the tablet or cleansing composition. For example, a tablet containing clay that was compressed prior to incorporation into the tablet will disintegrate more rapidly than a tablet containing the same clay material that has not been compressed prior to incorporation into the tablet. In particular, the amount of pressure used to compress the clay is important in order to obtain clay particles that help break up or disperse.

Furthermore, compressing the clay for softening and then incorporating it into a cleaning composition or tablet not only results in improved disintegration or dispersibility, it also softens fabrics very well. Preferably the clay component is obtained by compressing clay raw material.

Preferred methods include the step of compressing the clay raw material with a pressure of at least 10 MPa, or even at least 20 MPa or even 40 MPa. This step is accomplished, for example, by tableting or roller compacting the clay raw material, optionally with one or more other ingredients, to form clay tablets or flakes, preferably followed by, e.g. milling, making the compressed clay flakes or Tablets are reduced in size to form compressed clay granules. The granules can then be incorporated into tablets or cleaning compositions.

Tabletting methods and roll extrusion methods are known in the art. Compression of the clay can be accomplished, for example, on a Lloyd 50K tablet press or using a Chilsonator roll press from the Fitzpatrick Company.

In order that the present invention may be more readily understood, the following examples are arranged by reference. The examples are illustrative only and do not limit the scope thereof.

The following examples are presented for illustrative purposes only and are not to be construed as limiting the scope of the appended claims in any way.

abbreviation used in examples

In detergent compositions, the abbreviated component symbols have the following meanings:

LAS : Sodium linear C11-13 alkylbenzene sulfonate

TAS : sodium tallow alkyl sulfate

C45AS : Sodium C14-C15 Alkyl Sulfate

C45E3S: C14-C15 alkyl sulfate sodium salt condensed with 3 moles of ethylene oxide

QAS ：R2.N+(CH3)2(C2H4OH) where R2＝C12-C14

Soap: Linear alkyl carboxylic acids derived from an 80/20 blend of tallow and coconut fatty acids

Sodium

Zeolite A: hydrated sodium aluminosilicate with the chemical formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ 27H ₂ O

  Has a primary particle size ranging from 0.1 to 10 microns

(Weight expressed in dry weight)

NaSKS-6: a crystalline layer silicate with the chemical formula d-Na ₂ Si ₂ O ₅

Citric acid: anhydrous citric acid

Carbonate: anhydrous sodium carbonate, the particle size is 200μm～900μm

Bicarbonate: anhydrous sodium bicarbonate, the particle size distribution is 400μm～1200μm

Silicate: Amorphous sodium silicate (SiO ₂ :Na ₂ O=2.0:1)

Sulfate : Anhydrous Sodium Sulfate

Magnesium Sulfate: Anhydrous Magnesium Sulfate

Citrate: Trisodium citrate dihydrate, 86.4% active, particle size distribution is

    425μm～850μm

MA/AA : Copolymer of maleic acid/acrylic acid 1:4, average molecular weight about 70,000

AA : Sodium polyacrylate polymer, average molecular weight 4,500

CMC : Sodium Carboxymethyl Cellulose

Protease: proteolytic enzyme with 4% by weight active enzyme as described in WO 95/10591

As stated, sold by Genencor Int.Inc.

Cellulase: cellulolytic enzyme with 0.23% by weight active enzyme,

Sold by NOVO Industries A/S under the trade name Carezyme

Amylase: Amylolytic enzyme with 1.6% by weight active enzyme,

Sold by NOVO Industries A/S under the trade name Termamyl 120T

Lipase : lipolytic enzyme with 2.0% by weight active enzyme,

Sold by NOVO Industries A/S under the trade name Lipolase

Perborate: sodium perborate

Percarbonate: sodium percarbonate

NOBS : Nonanoyloxybenzenesulfonate, sodium salt form

NAC-OBS: (6-Nonanoylaminocaproyl)oxybenzenesulfonate

TAED : Tetraacetylethylenediamine

DTPA : Diethylenetriaminepentaacetic acid

EDDS : Ethylenediamine-N,N'-disuccinic acid in the form of the sodium salt, (S,S) isomer

Photosensitizer: sulfonated zinc phthalocyanine encapsulated in bleach(I) dextrin-soluble polymer

CHDM : 1,4-Cyclohexanedimethanol

Brightener: 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino)stilbene-2:2'-

    Disodium Disulfonic Acid

HEDP 1,1-Hydroxyethane diphosphonic acid

PEGx: polyethylene glycol, molecular weight x (typically 4,000)

QEA: Bis((C ₂ H ₅ O)(C ₂ H ₄ O) _n )(CH ₃ )-N ⁺ -C ₆ H ₁₂ -N ⁺ -(CH ₃ )bis((C ₂ H ₅ O)-

(C ₂ H ₄ O)) _n , wherein n=20～30

SRP : Diethoxylated poly(1,2-propanediol terephthalate) short block polymer

Silicone: Polydimethylsiloxane foam control agent with siloxane-oxyalkylene

Defoamer: as the copolymer of dispersant, the ratio of said foam control agent to said dispersant is

10:1～100:1

In the following examples all component levels are given in % by weight of the composition.

Example of liquid product preparation

Example I

A non-aqueous liquid detergent composition comprising a surfactant-rich liquid phase and a solid phase is prepared as follows:

weight%

Composition A Composition B

Non-ionic surfactant 21.27 20.14

BPP Solvent 18.30 17.33

LAS Surfactant 15.83 14.99

Ethoxylated quaternized amines 1.29 1.22

clay raw material

Hydrotrope 4.80 0.00

Sodium citrate dihydrate 6.73 6.37

Sodium carbonate 9.89 9.37

Bleach aid 5.94 5.62

Sodium perborate 11.87 11.24

EDDS 1.17 1.11

Duramyl enzyme 0.79 0.87

Carezyme enzyme 0.03 0.03

Protease 0.79 0.75

Defoamer 0.61 0.85

Plastic microspheres 0.51 0.49

Titanium dioxide 0.50 0.47

Brightener 0.20 0.19

PEG 8000 0.40 0.38

Spices 1.72 1.63

Other 2.16 2.15

Liquid detergent composition A is prepared according to the invention and therefore contains the preferred hydrotrope 1,4-cyclohexanedimethanol. As can be seen above, Liquid Detergent Composition B is almost identical to Composition A except that it does not contain the hydrotrope and its other components are slightly rebalanced.

The efficacy of the hydrotropes discussed herein can readily be seen by experimental testing to determine the rate of dissolution of liquid detergent compositions in water.

Test of Dissolving Speed of Liquid Detergent Products in Water

1. A glass beaker is filled with 3 liters of deionized water at approximately 25°C.

2. Put a 5cm magnetic stir bar and conductivity electrode in the water. The water was first mixed at a speed of 400 rpm and the speed was maintained throughout the experiment.

3. Place a sieve cup with a capacity of 85ml on the surface of the water in the middle of the beaker. The sieve cup has a 60-mesh screen. cup.

4. Very slowly add 1ml of liquid detergent product (via syringe) to the center of the sieve cup. This is T ₀ , the conductivity at T ₀ is measured.

5. Repeat the conductivity measurement of the detergent product-water mixture at regular intervals, such as 0.5, 1, 2, 4, 6 and 10 minutes.

6. After an appropriate time (eg 10 minutes), add the liquid detergent product remaining in the sieve cup to the product-water mixture by dipping the sieve cup into the mixture and increasing the stirring speed.

7. When all the product has dissolved and the conductivity has reached a steady state value, record said value.

These two compositions were tested using the " Test for Dissolution Rate of Liquid Detergent Products in Water " detailed above. Conductivity was measured with an electrode immersed in water at the beginning of the solution of the tested-detergent composition and at the transition to % dissolved, the following results were obtained:

After 11 minutes, use high-speed agitation to force the detergent composition to completely dissolve and measure the conductivity:

all dissolved 100 100 146 100

Dissolution values were obtained by dividing the conductivity measured at each individual time by the conductivity measured at total dissolution and multiplying by 100.

Example II

The preparation of the aqueous liquid detergent composition according to the present invention is as follows:

Composition C

Component weight %

C _12-15 alkyl ether (2.5) sulfate 18.0

C _12-13 Alkyl Ethoxylate (9.0) 2.00

C _12-14 Glucosamide 3.50

Citric acid 3.00

C _12-14 fatty acids 2.00

CHDM 5.00

MEA to pH 8

Ethanol 3.0

Propylene Glycol 6.0

dyes, fragrances, brighteners, enzymes, preservatives,

Foam suppressors, other minor components, water balance

100%

Example III

A non-aqueous liquid detergent composition comprising a surfactant-rich liquid phase and a solid phase is prepared as follows:

weight%

Composition Composition Composition Composition Composition Composition

A A B B C C D D E

NaLAS 14.6 14.9 13.9 13.0 14.9

HLAS 0.0 0.0 1.0 1.9 0.0

Non-ionic surfactant 20.6 20.7 20.7 20.7 20.7

Sodium citrate dihydrate 3.3 3.3 3.3 3.3 3.3

Acrylic maleic acid copolymer 2.9 2.9 2.9 2.9 2.9

EDDS 1.2 1.2 1.2 1.2 1.2

Ethoxylated quaternized 1.3 1.3 1.2 1.3 1.3

Amine Clay Raw Materials

Sodium perborate 11.5 11.5 11.5 11.5 11.5

Bleach aid 2.9 5.8 2.9 2.9 2.9

Triacetin 12.5 0.0 12.5 12.5 8.7

Sodium Carbonate 9.6 9.6 9.6 9.6 9.6

BPP Solvent 9.1 17.8 9.1 9.1 12.0

Hydrotrope 3.8 4.8 3.8 3.8 4.8

Acetic acid 0.2 0.0 0.1 0.0 0.0

Protease 0.8 0.8 0.8 0.8 0.8

Duramyl enzyme 0.8 0.4 0.4 0.4 0.4

Mannanase 0.2 0.2 0.2 0.2 0.2

Carezyme enzyme 0.1 0.0 0.0 0.0 0.0

Brightener 0.2 0.2 0.2 0.2 0.2

Titanium dioxide 0.5 0.5 0.5 0.5 0.5

PEG 8000 0.5 0.5 0.5 0.5 0.5

Spices 1.7 1.7 1.7 1.7 1.7

Siloxane 0.7 0.7 0.7 0.7 0.7

Silicone Surfactant 0.3 0.3 0.3 0.3 0.3

DC3225

Hydrogenated C16-18 fatty acid sodium salt 0.5 0.5 0.5 0.5 0.5

Others Balance Balance Balance Balance

Granular/powder product formulation example

Example I

The following are compositions according to the invention.

A B C D E F G h I spray dried granules LAS 10.0 10.0 15.0 5.0 5.0 10.0 - - - QAS 1.0 1.0 - - - DTPA, HEDP and/or EDDS 0.3 0.3 0.5 0.3 - - - MgSO₄ 0.5 0.5 0.1 - - - - Sodium citrate - - - 3.0 5.0 - - - Sodium carbonate 10.0 10 15 10 7 10 - - - sodium sulfate 5.0 5.0 - - 5.0 3.0 - - - Sodium silicate 1.6R - - - - 2.0 - - - Zeolite A 16.0 18.0 20.0 20.0 - - - - - SKS-6 - - - 3.0 5.0 - - - - MA/AA or AA 1.0 2.0 11.0 - - 2.0 - - - CHDM 0.5 2.0 2.5 1.5 4.0 1.0 - - - QEA 1.0 - - - 1.0 - - - - brightener 0.05 0.05 0.05 - 0.05 - - - - Silicone oil 0.01 0.01 0.01 - - 0.01 - - - Agglomerates LAS - - - - 0.2 0.2 0.01 C₄₅AS - - - - 2.0 - 1.0 AE₃ - - - - - 1.0 0.5 carbonate - - 4.0 1.0 1.0 1.0 - Sodium citrate - - - - - - 5.0 CFAA - - - - -

citric acid - - - 4.0 - 1.0 1.0 QEA - - - 2.0 2.0 1.0 - SRP - - - 1.0 1.0 0.2 - Zeolite A - - - 15.0 26.0 15.0 16.0 Sodium silicate - - - - - - - CHDM - - - - - - 3.0 - - builder agglomerates SKS-6 6.0 - - - 6.0 3.0 - 7.0 10.0 LAS 4.0 5.0 - - 5.0 3.0 - 1.0 12.0 dry addition of particulate components Malic acid/carbonate/bicarbonate (40:20:40) 8.0 - 10.0 4.0 - 8.0 - - 4.0 QEA - - - 0.2 0.5 - - - - NACAOBS 3.0 - - 1.5 - - - 2.5 - NOBS - 3.0 3.0 - - - - - 5.0 TAED 2.5 - - 1.5 2.5 6.5 - 1.5 - LAS (thin slice) 10.0 10.0 - - - - - 8.0 - spray brightener 0.2 0.2 0.3 0.1 0.2 0.1 - 0.6 - Dye - - - 0.3 0.05 0.1 - - - AE7 - - - - - 0.5 - 0.7 - Spices - - - 0.8 - 0.5 - 0.5 - dry plus

Citrate - - 20.0 4.0 - 5.0 15.0 - 5.0 Percarbonate 15.0 3.0 6.0 10.0 - - - 18.0 5.0 Perborate - - - - 6.0 18.0 - - - Photobleaching 0.02 0.02 0.02 0.1 0.05 - 0.3 - 0.03 Enzymes (cellulase, amylase, protease, lipase) 1.3 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 carbonate 0.0 10.0 - - - 5.0 8.0 10.0 5.0 Spices (enclosed in capsules) 0.6 0.5 0.5 - 0.3 0.5 0.2 0.1 0.6 Antifoam 1.0 0.6 0.3 - 0.10 0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 - - 0.3 - citric acid - - - 6.0 6.0 - - - 5.0 Dyed carbonates (blue, green) 0.5 0.5 1.0 2.0 - 0.5 0.5 0.5 1.0 SKS-6 - - - 4.0 - - - 6.0 - Add filler to 100%

At least 90% by weight of the particles of the compositions of the above examples have a geometric mean particle diameter of about 850 microns and a geometric standard deviation of about 1.2. These compositions have unexpectedly improved aesthetics, flow and solubility.

Tablet product preparation example

Example 1a

i) Detergent Base Powder Composition A (see Table 1) was prepared as follows: All particulate materials of Base Composition A were mixed together in a mixing drum to form a homogeneous particulate mixture.

ii) Spray 1 part polyethylene glycol into 99 parts Base Powder Composition A while mixing.

iii) Tablets were made in the following manner: 54 g of the mixture was transferred into a circular mold with a diameter of 5.5 cm and compressed with an Instron 4464 press at a pressure of 2.0 kN. The tablet tensile strength (or radial crushing pressure) obtained at this pressure was 19.2 kPa. Pharmaceutical Dosage Forms: Tablets, Vol. 1, edited by H.A. Lieberman et al., published 1989, gives a method for assessing tablet strength (also called radial crushing pressure).

Example 1b

i) The same composition A was prepared in the same manner as in Example 1a.

ii) 0.9 parts of polyethylene glycol and 0.1 parts of 1,4-cyclohexanedimethanol were mixed together and sprayed into 99 parts of Base Powder Composition A while mixing.

iii) Tablets were prepared in the same manner as described in Example 1a. The tablet tensile strength (or radial crushing pressure) obtained under a pressure of 2.0 kN was 23.6 kPa.

Examples 2a-3b were prepared in a manner analogous to the method described above according to the following detailed composition formulations:

Table 1

Composition A Composition B Composition C (%) (%) (%) Anionic agglomerates¹ 34 34 34 Non-ionic agglomerates² 9.57 9.57 9.57 Layer silicate ³ 2.7 1.5 1.5 Sodium percarbonate 12.43 12.43 12.43 Bleach aid agglomerates⁴ 6.48 6.48 6.48 Sodium carbonate 19.01 18.96 18.46 EEDS/Sulphate Granules⁵ 0.50 0.50 0.50 Hydroxyethane diphosphonic acid tetrasodium salt 0.8 0.8 0.8 Fluorescent whitening agent 0.11 0.11 0.11 Zinc Phthalocyanine Sulfonate Capsules⁶ 0.027 0.027 0.027 soap powder 1.49 0.74 0.74 Foam inhibitor ⁷ 1.8 1.8 1.8 citric acid 7.51 7.51 7.51 protease 0.8 0.8 0.8 cellulase 0.16 0.16 0.16 Amylase 0.61 0.61 0.61 Polyethylene glycol, molecular weight 4000, flakes - 1.5 1.5 Sodium linear alkylbenzenesulfonate/diisopropylbenzenesulfonate⁸ 1 1 1.5

1: Anionic agglomerate comprising 37% anionic surfactant, 2% cationic surfactant, 22% layer silicate, 10% acetate, 6% carbonate and 23% zeolite.

2: Nonionic agglomerates containing 24% nonionic surfactant, 6% ethoxylated hexamethylenediamine quaternary ammonium salt, 40% acetate/zeolite mixture, 20% carbonate and 10% zeolite .

3: Layer silicate, containing 95% SKS 6 and 5% silicate.

4: Bleach aid agglomerates comprising 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.

5: Ethylenediamine-N,N-disuccinate sodium salt/sulfate granules containing 58% ethylenediamine-N,N-disuccinate sodium salt, 23% sulfate and 19% water.

6: 10% active zinc phthalocyanine sulfonate capsules.

7: Suds suppressor comprising 11.5% silicone oil (available from Dow Coming), 59% zeolite and 29.5% water.

8: Sodium linear alkylbenzenesulfonate/diisopropylbenzenesulfonate containing 67% linear alkylbenzenesulfonate and 33% diisopropylbenzenesulfonate.

Spray the tablet binder composition according to the following combination into the above detergent base powder:

Table 2

Example 1a Example 1b Example 2a Example 2b Example 3a Example 3b Powder A 99% 99% Powder B 98.5% 98.5% Powder C 98.5% 98.5% polyethylene glycol 1% 0.9% 1.50% 1.35% 1.5% 1.3% 1,4-Cyclohexanedimethanol 0.1% 0.15% 0.2%

The tablets were then tested for strength as described in step iii) above and elsewhere in this disclosure.

table 3

Example 1a Example 1b Example 2a Example 2b Example 3a Example 3b Tablet tensile strength (kPa) 19.2 23.6 12.4 14.7 16 19

The tensile strength of the tablet samples containing CHDM was greater than the CHDM tablet samples of virtually the same composition but without CHDM.

Also evaluate the operating limits:

Table 4

Example 3a Example 3b Density when tablet hardness is 5.5kP 1035 1010 Density of tablet at 15% dose 1052 1035

Tablet samples containing CHDM (width = 25 g/l) had wider operating limits than those without CHDM (width = 17 g/l).

The detergent tablet doses listed in Table 4 above may be determined by experimental testing which measures the amount of detergent product dispensed during an automatic wash process in the following manner:

WA9850洗涤机的给料器中，供给洗涤机的水的温度设定为20℃，及硬度为每加仑21格令，给料器水入口流动-速度设定为8l/min。1. Weigh two tablets of nominally 50 grams each and place in the Baucknecht

In the feeder of the WA9850 washing machine, the temperature of the water supplied to the washing machine was set at 20°C, and the hardness was 21 grains per gallon, and the feeder water inlet flow-velocity was set at 8 l/min.

2. Switch on the wash and set the wash cycle to wash program 4 (white/coloured, short cycle), check the weight of the tablet residue left in the feeder.

3. The amount of residue in percent dose is determined as follows:

% dose = residue weight x 100/starting tablet weight

The procedure was repeated 10 times to determine the residue amount and the average residue amount was calculated based on ten individual measurements.

Having thus described the invention in detail, it will be apparent to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not considered to be limited by what has been described in the specification.

Claims (9)

1. non-aqueous liquid laundry detergents composition, it comprises:

A) press composition weight meter, 49%～99.95% non--water-based liquid phase that contains tensio-active agent; And

B) press composition weight meter, 1%～50% the particulate starting material that is insoluble to said liquid phase basically, particulate starting material are selected from peroxygen bleach, bleach activator, organic detergent washing assistant, inorganic alkali source, enzyme, brightener, polymkeric substance and their mixture;

C) hydrotropic agent, wherein hydrotropic agent is selected from:

(a) 1,4 cyclohexane dimethanol:

(b) 1, the 6-hexylene glycol:

(c) 1, the 7-heptanediol:

With

(d) their mixture,

And

Wherein composition does not contain any following compounds deutero-quaternary ammonium compound: C _16-18Unsaturated fatty acids, methyldiethanolamine or methyl chloride.

2. according to the non-aqueous liquid laundry detergents composition of claim 1, wherein the further feature of detergent composition is that its composition is selected from: nonionic surface active agent; Be selected from the organic additive of Vanay, Triethyl citrate acetate or their mixture; Enzyme; Quaternized amine raw material of ethoxylation and their mixture.

3. according to the non-aqueous liquid detergent compositions of claim 1, wherein detergent composition contains 0.01%～10% fabric care agent.

4. according to the non-aqueous liquid detergent compositions of claim 1, non--the density that the water-based liquid phase has that wherein contains tensio-active agent is 0.6～1.4 gram/cubic centimetre.

5. according to the non-aqueous liquid detergent compositions of claim 4, wherein the granular size that has of particulate starting material is 0.1～1500 micron.

6. according to the non-aqueous liquid detergent compositions of claim 1, it further comprises median particle size is 10 microns～150 microns microsphere.

7. according to the non-aqueous liquid detergent compositions of claim 6, it comprises the microsphere that mean density is 0.1 grams per milliliter～1.8 grams per milliliters.

8. the method for a contamination with wash fabric, it comprises the step that said fabric is contacted with non-aqueous liquid detergent compositions according to claim 1 in the water-based washing soln.

9. the method for a contamination with wash fabric, it comprises the step that said fabric is contacted with laundry detergent composition according to claim 3 in the water-based washing soln.