JP2003506560A - Detergent compositions containing hydrotropes - Google Patents

Abstract

  (57) [Summary] The present invention relates to improved hydrotrope-containing detergent compositions, in particular liquid, granule and tablet forms, wherein the hydrotrope is an organic molecule in which at least 5 aliphatic carbon atoms and two polar groups are separated from one another. Liquid compositions containing such hydrotropes have viscosities, dilution properties and elution behavior that make the product effective and convenient to use as a liquid laundry detergent composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION

The invention relates to detergent compositions containing improved hydrotropes, in particular liquid, granule and tablet forms, wherein the hydrotrope is an organic molecule in which two polar groups are separated from each other by at least 5 aliphatic carbon atoms. The liquid composition containing such a hydrotrope has viscosity, dilution characteristics and elution behavior that make the product effective and convenient for use as a liquid laundry detergent composition.

[0002]

BACKGROUND OF THE INVENTION

In recent years, the popularity of detergent products in forms other than granules / powder has increased. These other forms include liquids and tablets. Liquid laundry detergent products exhibit some advantages over dry, powdered or granular laundry detergent products. Liquid laundry detergent products are easy to weigh, dissolve quickly in the wash water, do not splash, can be easily applied as a concentrated solution or dispersion to the dirty parts of the clothes being washed, and usually have less storage space than granular products. It's done. In addition, liquid laundry detergents may incorporate into their formulation materials that may be degraded by the drying operations used to make granular or granular laundry detergent products. They are substantially preferred by consumers because liquid laundry detergents usually appear to be easier to use than granular laundry detergents. Despite the advantages of liquid detergent compositions, granular products retain many advantages.
These advantages include performance, formulation capability, low cost packaging and high product stability. The advantages of product stability and formulation ability are that before being mixed with other particles,
Mostly derived from the nature of the granule mixture, where the components are individually stabilized and divided into particles. Because of this physical separation in the final detergent composition, potentially labile substances such as bleach, enzymes, etc. can be used in the composition.

It is well known to produce a detergent composition in tablet form by compressing a granular detergent composition. Such tablets do not have the inconvenience and hassle of weighing sufficient granular detergent composition for each wash, and provide the consumer with the convenience that the detergent usage has already been measured. Such products also offer considerable convenience to consumers who wash their clothes outdoors or away from their home (eg, in a laundromat), as long as they need to wash their clothes. This is because all that is required is to carry the detergent properly. The detergent composition may be manufactured in tablet form by pressing detergent granules.

A drawback with conventional liquid detergent compositions has been the compatibility of the ingredients. Granules and /
Alternatively, laundry detergent ingredients that are compatible with one another in a tablet product tend to interact or react with each other in a liquid, especially an aqueous liquid environment. A drawback with the granule / powder detergent composition was the relatively poor elution, dispersion and dissolution performance. A drawback with conventional tablet detergent compositions is that they make the tablet strong and durable enough to avoid breakage during manufacture, shipping and / or storage, while at the same time the tablet is in contact with wash water. It was a conflict to make tablets that would disintegrate rapidly.

Thus, not only did it have excellent cleaning performance and composition and physical stability, but also had viscosity, dilution characteristics and elution behavior that made it useful and convenient for use as a liquid laundry detergent composition. There is an ongoing need to provide / formulate liquid detergent compositions; granule / powder detergent compositions with improved elution, dispersion and dissolution performance while maintaining the formulation flexibility inherent in granule / powder detergents. There is an ongoing need to provide / formulate products; strong and durable enough to withstand breakage during manufacture, transport and / or storage, and rapidly disintegrate upon contact with wash water to produce tablets. There is a continuing need to provide / formulate tablet detergent compositions in which the ingredients can exert a cleaning effect during the cleaning process.

[0006]

[Summary of Invention]

Addition of certain hydrotropes to the detergent compositions of the present invention, such as aqueous or non-aqueous liquid laundry detergent compositions, granule / powder laundry detergent compositions and / or tablet laundry detergent compositions, results in 1) products as liquid laundry detergent compositions. Viscosity, which makes it useful and convenient
Liquid detergent products with diluting properties and elution behavior, and / or 2) improved dispersion with the need to reduce surfactant levels compared to granular / powder detergent products lacking such hydrotropes, Granule / powder detergent compositions having elution and / or dissolution performance, and / or 3) improved strength and durability with superior disintegration and elution properties as compared to tablet detergent products lacking such hydrotropes. It has been discovered in the present invention that hydrotropes with properties can provide tablet detergent products useful as binders. A. Liquid Products Liquid detergent products containing these hydrotropes exhibit excellent cleaning performance, excellent composition and physical stability, and favorable product rheological behavior. Some of these hydrotropes are most commonly classified as organic molecules in which two polar groups are separated from each other by at least 5 aliphatic carbon atoms. Liquid detergent products may be aqueous or non-aqueous. As a preferable aspect of the present invention,
A hydrotrope in which two polar groups are separated from each other by at least 5 aliphatic carbon atoms,
About 49 to about 99.95% by weight of the composition of a non-aqueous liquid phase containing a surfactant, and about 1 to about 50% by weight of the composition, which is substantially insoluble in the above liquid phase and is a peroxygen. There is provided a non-aqueous liquid detergent containing a particulate material selected from bleach, bleach activator, organic detergent builders, inorganic alkalinity sources and combinations thereof.

B. Granule / Powder Products Granule / powder detergent products containing these hydrotropes have improved dispersion with the need to reduce surfactant levels as compared to granule / powder detergent products lacking such hydrotropes. , Elution and / or dissolution performance. Most of these hydrotropes are generally 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 made in accordance with the present invention are generally classified as binders in which organic molecules have a first polar group and a second polar group separated from each other by at least 5 aliphatic carbon atoms. It contains a hydrotrope (“binder”) that is characterized in that Tablet detergent products exhibit improved strength and durability with superior disintegration and elution properties as compared to tablet detergent products lacking such hydrotropes.

[Chemical 4]

All parts, percentages and ratios used herein are expressed as weight percent unless otherwise noted. All references cited are, in relevant part, hereby incorporated by reference.

[0010]

Detailed Description of the Invention Definitions "Hydrotrope" -As used herein, a "hydrotrope" is a compound with the ability to increase the solubility, preferably the aqueous solubility, of a somewhat soluble organic compound. And more preferably "hydrotrope" is defined as follows (SEFriberg and M. Chiu, J. Dispersion Science and Technology, 9 (5 & 6),
pages 443-457 (1988-1989)): Prepare a solution consisting of 1.25% by weight of the specified compound and 75% by weight of water. 2. Octanoic acid is then added to the solution in a ratio of 1.6 times by weight of the specific compound in the solution, the temperature of the solution being 20 ° C. The solution is mixed in a Sotax beaker with a stirrer equipped with a marine propeller, the propeller being located about 5 mm above the bottom of the beaker and the mixer being set at a rotation speed of 200 rpm. 3. If the octanoic acid is completely dissolved, ie the solution consists of only one phase and that phase is the liquid phase, the particular compound is a hydrotrope.

“Non-aqueous” or “anhydrous” -as used herein “non-aqueous” or “anhydrous”
Are used as synonyms and both represent fluids with free water of less than about 1%. "Polar group" -As used herein, "polar group" refers to a functional group having a permanent electric dipole moment resulting from a local charge at atoms connected by a polar bond. The polar group itself may be negatively charged or uncharged. "Elution" -As used herein, "elution" refers to the phenomenon that a detergent product mixes with water to release the active ingredient during washing.

[0012] "particles" - the term by which "particles" as used herein, the detergent final product or constituent of all sizes range or final detergent product or individual particles of all size ranges in the constituent mixture, aggregates Or means granules. Unless the size fraction represents 100% of the individual particles in the mixture of particles, it is not particularly relevant to the size fraction of any of these types of particles (ie representing less than 100% of the total size range). For each type of particle component in the mixture, individual particles of the entire size range of that type have the same or substantially similar composition, whether or not the particles are in contact with other particles. In the case of agglomerated constituents, the agglomerates themselves are considered as individual particles, and each individual particle may be composed of a composite of small primary particles and a binder composition.

[0013] "geometric mean particle diameter" - the phrase by which "geometric mean particle diameter" used here, any of the standard mass-based particle size measurement technique, preferably as measured by dry sieving, series Means the geometric mass median diameter of each individual particle. "Geometric standard deviation" or "span" -"geometric standard deviation" as used here
Alternatively, the phrase "span" means the geometrical width of the lognormal function that best fits the particle size data above, which is 84.1 divided by the diameter of the 50 ^{th percentile} of the cumulative distribution.
Obtained by the ratio of the percentile diameters (D _84.13 / D ₅₀ ); Gotoh et al., Powd
er Technology Handbook, pp. 6-11, Marcel Dekker, 1997.

Hydrotropes The hydrotropes described in this section are an essential component of the detergent composition. It has been discovered in the present invention regarding the effect of the addition of a hydrotrope in which two polar groups are separated from each other by at least 5, preferably 6 aliphatic carbon atoms. Examples of suitable polar groups for introduction into the hydrotrope are hydroxyl and carboxyl ions. A particularly preferred hydrotrope is 1,4-cyclohexanedimethanol:

[Chemical 5] 1,6-hexanediol:

[Chemical 6] 1,7-Heptanediol:

[Chemical 7] And a mixture thereof. Mixtures of several of these organic molecules, or hydrotrope molecules having two polar groups separated from each other by at least 5, preferably 6, aliphatic carbon atoms are also acceptable. The 1,4-cyclohexanedimethanol can be present in its cis form, its trans form or a mixture of both forms.

A. Liquid product The present invention relates to an aqueous or non-aqueous liquid laundry detergent composition suitable for automatic washing machines or for pre-treating stains and stains on textiles or textiles before washing. The liquid laundry detergent compositions may contain only a surfactant-rich liquid phase, or they may contain both a surfactant-rich liquid phase and a solid particulate phase suspended in the liquid phase. Preferably, the surfactant-rich liquid phase comprises a hydrotrope and optionally an organic diluent. The hydrotrope of the present invention is an important ingredient in preventing gelation and / or thickening of the liquid detergent composition disclosed herein when incorporated into the liquid product of the present invention.

Gelation was already observed in liquid detergent products made without a hydrotrope as defined in this invention when the product was first contacted with water and diluted. Without being bound by theory, this gelation phenomenon is the result of a viscous surfactant phase (typically a lamella, spherulite or hexagonal phase) being washed at a concentration of surfactant and water. It is thought that this is because the system forms. There is a correlation between the viscosity of the product: water mixture in the critical dilution range where gelation is observed and the amount of viscous surfactant phase formed.

In a preferred embodiment, the detergent composition is non-aqueous and has a non-aqueous liquid phase rich in surfactant and a solid particulate phase suspended in the liquid phase. In this aspect, the surfactant-containing non-aqueous liquid phase typically comprises about 49 to 99.95% by weight of the detergent composition.
Is. Even more preferably, the liquid phase is surfactant structured and comprises about 5% of the composition.
It is 2 to 98.9% by weight. Most preferably, the non-aqueous liquid phase is about 5% of the composition.
5 to 70% by weight. Such a surfactant-containing liquid phase is usually about 0.6 to 1.4.
It has a density of g / cc, more preferably about 0.9-1.3 g / cc.

Without being bound by theory, hydrotropes effectively interact with the ordered layers of surfactant molecules, destroying them and promoting the formation of an isotropic low viscosity surfactant phase. Therefore, it is considered that the above hydrotrope can prevent the formation of a viscous surfactant phase formed by dilution. These hydrotropes also have other effects in improving the rheology of liquid detergent compositions. For example, ethoxylated quaternary amine materials cause ionic ethoxylation in detergent compositions containing anionic surfactants, as they precipitate anionic surfactants from the liquid phase and significantly thicken liquid detergent compositions. It is generally difficult to incorporate a quaternary amine material. Nonetheless, it is highly desirable to incorporate them into liquid detergent products because of the significant performance benefits of these dirt remover / redeposition inhibitors. Inclusion of the above hydrotropes avoids the commonly observed precipitation of anionic surfactants and thickening of the composition,
It has been observed in the present invention that a liquid detergent composition with desirable rheological properties is produced. Ethoxylated quaternary amine materials are described in further detail below.

The liquid surfactant-containing liquid phase present liquid detergent composition phase is formed preferably less hydrotrope, nonionic and anionic surfactants, and one or more organic diluent.

[Chemical 8]

Organic Diluent- The main component of the liquid phase of the present detergent composition comprises one or more aqueous or non-aqueous organic diluents. The organic diluents used in the present invention are surface-active liquids, ie, non-surfactant liquids which are also surfactants, or herein referred to as solvents. "solvent"
The term is used herein to mean the non-surfactant liquid portion of the composition. Some of the essential and / or optional components of the composition are actually soluble in the "solvent" containing liquid phase, while other components are present as particulate material dispersed within the "solvent" containing liquid phase. Thus, the term "solvent" does not require that the solvent material be capable of actually dissolving all the detergent composition ingredients added thereto. The liquid diluent component is usually about 50-90%, more preferably about 50-80%, most preferably about 55-75% of the surfactant-containing liquid phase that is constructed. Preferably, the liquid phase of the composition consists of both liquid surfactant and non-surfactant solvent.

I) Surfactant liquids-Suitable types of surfactant liquids that can be used to form the liquid phase of the composition include alkoxylated alcohols, ethylene oxide (EO).
-Propylene oxide (PO) block polymers, polyhydroxy fatty acid amides, alkyl polysaccharides and the like. Such normally liquid surfactants have an HLB in the 10-16 range. Most preferred of the surfactant liquids are alcohol alkoxylate nonionic surfactants.

Alcohol alkoxylates are substances corresponding to the following general formula: R ¹ (C _m H _2m O) _n OH In the above formula, R ¹ is a C ₈ -C ₁₆ alkyl group and m is 2-4. Yes, n is about 2
Twelve. Preferably, R ¹ is a primary or secondary alkyl group and comprises about 9-
It has 15 carbon atoms, more preferably about 10-14 carbon atoms. Preferably, the alkoxylated fatty alcohol is an ethoxylated material having about 2 to 12 ethylene oxide moieties per molecule, more preferably about 3 to 10 ethylene oxide moieties per molecule. The alkoxylated fatty alcohol materials useful in the liquid phase typically have a hydrophilic-lipophilic balance (HLB) in the range of about 3-17. More preferably, the HL of this substance
B is in the range of about 6-15, most preferably about 8-15.

Examples of fatty alcohol alkoxylates useful as or in the liquid phase of the composition are those made from alcohols having 12 to 15 carbon atoms and having about 7 moles of ethylene oxide. Such materials are commercially available from Shell Chemical Company under the trade names Neodol 25-7 and Neodol 23-6.5. Other useful Neodols are ethoxylated fatty alcohols having an average of 11 carbon atoms in their alkyl chains with about 5 moles of ethylene oxide, Neodol 1-5; ethoxylated primary C ₁₂ -C ₁₃ with about 9 moles of ethylene oxide. There is an alcohol, Neodol 23-9; and an ethoxylated C _9- C ₁₁ primary alcohol, Neodol 91-10, having about 10 moles of ethylene oxide. This type of alcohol ethoxylate is also available in Shell Chem
It is sold by ical Company under the trade name Dobanol. Dobanol 91-5 is an ethoxylated C ₉ -C ₁₁ fatty alcohol with an average of 5 moles of ethylene oxide,
Dobanol 25-7 is an ethoxylated C ₁₂ -C ₁₅ fatty alcohol having an average of 7 moles ethylene oxide per mole fatty alcohol.

Other examples of suitable ethoxylated alcohols are Tergitol 15-S-7 and Tergitol
15-S-9, both of which are linear secondary alcohol ethoxylates commercially available from Union Carbide Corporation. The former is a mixed ethoxylation product of C ₁₁ -C ₁₅ linear secondary alkanols with 7 moles of ethylene oxide, the latter 9
Analogous product reacted with moles of ethylene oxide. Another type of alcohol ethoxylate useful in the present composition is a high molecular weight nonionic system such as Neodol 45-11, which is a similar ethylene oxide condensation product of a higher fatty alcohol, the higher fatty alcohol being 14-15. 1 carbon atom
The number of ethylene oxide groups per mole is about 11. Such products also Shell
Commercially available from Chemical Company.

If an alcohol alkoxylate nonionic surfactant is utilized in the detergent composition as part of the liquid phase, it is preferably present to the extent of about 1-60% of the composition-building liquid phase. More preferably, the alcohol alkoxylate component is about 5-40% of the build liquid phase. Most preferably, the alcohol alkoxylate component is about 5-35% of the detergent composition build liquid phase. Utilization of alcohol alkoxylates at these concentrations in the liquid phase is about 1-60% by weight of the composition, more preferably about 2-40.
Corresponds to a weight percent, most preferably about 5 to 25 weight percent alcohol alkoxylate concentration in the total composition.

Another type of surfactant liquid that can be utilized in the present invention is an ethylene oxide (EO) -propylene oxide (PO) block polymer. This type of material is a well known nonionic surfactant sold under the trade name Pluronic.
These materials are formed by adding blocks of ethylene oxide moieties to the ends of polypropylene glycol chains to adjust the surface activity of the resulting block polymers. This type of EO-PO block polymer nonionic system is
vidsohn and Milwidsky, Synthetic Detergents, 7th Ed. , Longman Scientific an
d Technical (1987), pp.34-36 and pp.189-191 and US Patent 2,674,619.
And 2,677,700. All these documents are incorporated herein by reference. It is believed that these Pluronic-type nonionic surfactants also function as effective suspending agents for the particulate material dispersed in the liquid phase of the detergent composition.

Another possible type of surfactant liquid useful in the composition is a polyhydroxy fatty acid amide surfactant. This type of nonionic surfactant material corresponds to the formula:

[Chemical 9] In the above formula, R is C _9-17 alkyl or alkenyl, p is 1 to 6, and Z is glycityl derived from a reducing sugar or an alkoxylated derivative thereof. Such materials include _C 12 _-C 18 N-methyl glucamides. Example is N-methyl
N-1-deoxyglusityl cocoamide and N-methyl N-1-deoxyglusityl oleamide. Methods for producing polyhydroxy fatty acid amides are known, for example Wilson US Pat. No. 2,965,576 and Schwartz US Pat.
703, 798, the disclosure of which is incorporated herein by reference. The substance itself and their manufacturing method are also US of Honsa issued on December 26, 1992.
Further details are provided in US Pat. No. 5,174,937, which is also incorporated herein by reference.

The detergent composition of the present invention may also contain anionic, cationic and / or amphoteric types. In the preferred embodiment where the liquid phase is non-aqueous, the liquid phase is usually, but not necessarily, described in the present invention as a surfactant selected to add buildability to the non-aqueous liquid phase of the detergent composition. It is prepared by mixing with the diluted non-aqueous organic liquid. Build-up surfactants can be anionic, nonionic, cationic and / or amphoteric types. Thus, the surfactants described below may be added solely for their surface-active attributes, or for that attribute and their buildability.

Preferred surfactants are anionic surfactants such as alkyl sulphates, alkyl polyalkoxylate sulphates and linear alkyl benzene sulphonates. Another general type of anionic surfactant material that is optionally added to the present detergent composition as a builder comprises a carboxylate-type anionic system. The carboxylate-type _anionic, C 10 _{-C 18} alkyl alkoxy carboxylates (especially, EO1～5 ethoxy carboxylate) and _C 10 _{-C 18} sarcosinates, especially oleoyl sarcosinate. Yet another general type of anionic surfactant material used as a builder is other sulfonated anionic surfactants such as C ₈ -C ₁₈ paraffin sulfonates and C ₈ -C ₁₈ olefin sulfonates. . The build-up anionic surfactant is typically about 1-30% by weight of the composition. As mentioned above, one preferred type of structured anionic surfactant comprises a primary or secondary alkyl sulphate anionic surfactant. Such surfactants are those produced by the sulfation of higher C ₈ -C ₂₀ fatty alcohols.

[0030] Conventional primary alkyl sulfate surfactants have the following general formula: ROSO ₃ ^- M ⁺ in the above formula R is typically a linear or branched linear _C 8 _{-C 20} in It is a hydrocarbyl group and M is a water-soluble cation. Preferably R is C _10-14 alkyl and M is an alkali metal. Most preferably, R is about _{C 12,} M is sodium. Conventional secondary alkyl sulphates may also be utilized as build-up anionic surfactants for the liquid phase of the composition. If utilized, the alkyl sulfate is typically about 1 to 30% by weight of the composition,
More preferably, it is about 5 to 25% by weight of the composition. A non-aqueous liquid detergent composition containing an alkyl sulphate, a peroxygen bleaching agent and a bleach activator is disclosed in Kong-Chan et al. WO 96/10073 published April 4, 1996.
Are described in more detail in, and the application is incorporated herein by reference.

Another preferred type of anionic surfactant material that is optionally added to the present non-aqueous cleaning compositions consists of alkyl polyalkoxylate sulphates. Alkyl polyalkoxylate sulphates are also known as alkoxylated alkyl sulphates or alkyl ether sulphates.
Such materials are those corresponding to the following ^{_{formula: R 2 -O- (C m H}} 2m O) n -SO 3 M above wherein ^{R 2} is _C 10 _{-C 22} alkyl group, m is 2 ~ 4 and n is about 1
~ 15 and M is a salt-forming cation. Preferably, R ² is C ₁₂ -C ₁₈ alkyl, m is 2, n is about 1-10, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium. Most preferably R ² is C ₁₂ -C ₁₆ , m is 2 and n is about 1
~ 6 and M is sodium. Ammonium, alkylammonium and alkanolammonium counterions are incompatible with the peroxygen bleach when used in the composition and are preferably avoided. If utilized, the alkyl polyalkoxylate sulphate is also typically about 1 to 30% by weight of the composition, more preferably about 5 to 25% by weight of the composition. Non-aqueous liquid detergent compositions containing an alkyl polyalkoxylate sulphate in combination with a polyhydroxy fatty acid amide are described in Boutique et al. PCT application PCT / US9.
6/04223, which is incorporated herein by reference.

The most preferred type of anionic surfactant for use as a builder in the composition is a linear alkylbenzene sulfonate (LAS) surfactant. In particular, such LAS surfactants may be formulated into a particular type of anionic surfactant containing powder that is particularly useful for incorporation into the non-aqueous liquid detergent compositions of the present invention. Such powders consist of two separate phases. One of these phases is insoluble in the non-aqueous organic liquid diluent used in the composition and the other phase is soluble in the non-aqueous organic liquid. It is the insoluble phase of this preferred anionic surfactant-containing powder, which can be dispersed in the preferred non-aqueous liquid phase of the present composition to stabilize other added solid particulate matter in the composition in the final product. Form a network of agglomerated small particles that can be suspended.

For a more detailed description of suitable surfactants and methods of making such surfactants, 09 / 202,964, P & G Case, filed Dec. 23, 1998, incorporated herein by reference. No. See the co-pending application of Jay I. Kahn et al. Entitled "Preparation of Non-Aqueous Particulate-Containing Liquid Detergent Composition with Surfactant Constructed Liquid Phase" having 6150.

Typically, the liquid surfactant is about 25-70% of the liquid phase of the composition. More preferably, the liquid surfactant is about 30-65% of the construction liquid phase. This corresponds to a liquid surfactant concentration in the total composition of about 10-70% by weight of the composition, more preferably about 20-50%. Preferred Surfactant Construction The amount of total liquid surfactant in the non-aqueous liquid phase is as described above and is determined by the type and amount of the other composition ingredients and the desired composition properties.

Ii) Non-Surfactant Non-Aqueous Organic Solvents- The liquid phase of the detergent composition may also include one or more non-surfactant organic solvents. Such non-surfactant liquids are preferably of low polarity. For purposes of this invention, a "low polarity" liquid is one that has a tendency to dissolve one of the preferred types of particulate material used in the composition: peroxygen bleach, sodium perborate or sodium percarbonate. However, it refers to the ones that I have very little. Therefore, it is preferable not to use a relatively polar solvent such as ethanol. Suitable types of low polar solvents useful in the present liquid detergent compositions include alkylene glycol mono-lower alkyl ethers, low molecular weight polyethylene glycols, low molecular weight methyl esters and amides.

[0036] Low polar solvent used on the preferred type in this composition, there is a C ₄ -C ₈ branched or straight chain alkylene glycols. Materials of this type include hexylene glycol (4-methyl-2,4-pentanediol), 1,3-butylene glycol and 1,4-butylene glycol.

[0037] Here, the low-polarity solvent for use on another preferred type is mono-, di-, tri- or _tetra-C 2 -C ₃ alkylene glycol mono _C 2 -C ₆ alkyl ethers. Specific examples of such compounds are diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether and butoxy-propoxy-propanol (BPP) are particularly preferred.
Compounds of that type are marketed under the trade names Dowanol, Carbitol and Cellosolve.

Another preferred type of low polarity organic solvent useful herein comprises low molecular weight polyethylene glycol (PEG). Such materials have a molecular weight of at least about 150. Most preferred is PEG with a molecular weight of about 200-600. Yet another preferred type of non-polar solvent consists of low molecular weight methyl esters. Such materials are of the general formula: R ¹ -C (O) -OCH _{3 where} R ¹ is 1 to about 18. Examples of suitable low molecular weight methyl esters are methyl acetate, methyl propionate, methyl octanoate and methyl dodecanoate.

The normally less polar, non-surfactant organic solvent used is, of course, compatible and non-reactive with other composition components used in the liquid detergent composition, such as bleach and / or activator. Should be Such solvent components are preferably utilized in an amount of about 1 to 70% by weight of the liquid phase. More preferably, the low polarity non-surfactant solvent is about 10-60% by weight of the build liquid phase, most preferably about 20-50% by weight of the build liquid phase of the composition. Utilization of non-surfactant solvents at these concentrations in the liquid phase
It corresponds to a non-surfactant solvent concentration in the total composition of about 1 to 50% by weight of the composition, more preferably about 5 to 40% and most preferably about 10 to 30%.

Iii) Surfactant and non-surfactant solvent blend -in a preferred embodiment using both non-aqueous surfactant liquid and non-aqueous non-surfactant solvent, in a surfactant-containing liquid phase constructed The ratio of surfactant to non-surfactant liquid in, such as the ratio of alcohol alkoxylate to low polar solvent, can be used to modify the rheological properties of the final formed detergent composition. Generally, the weight ratio of surfactant liquid to non-surfactant organic solvent is about 50: 1 to 1:50. More preferably, this ratio is about 3: 1 to 1: 3, most preferably about 2: 1 to 1: 2.

[Chemical 10]

Solid Particulate Matter In addition to the surfactant-containing liquid phase, the present liquid detergent compositions also preferably contain about 1 to 50% by weight of the added solid phase particulate material dispersed and suspended in the liquid phase, and further. Preferably about 2
9 to 44% by weight. Generally, such particulate materials have a size of about 0.1-150.
It is 0 micron, more preferably about 0.1 to 900 microns. Most preferably, such materials are about 5-200 microns in size.

The additive particulate matter utilized herein consists of one or more types of detergent composition ingredients that are substantially insoluble in the liquid phase of the composition in particulate form. Such materials include peroxygen bleaches, bleach activators, organic detergent builders, inorganic alkali sources and combinations thereof. The types of particulate materials that can be utilized are described in detail below, however, some materials may be included in either the particulate component or the surfactant-containing liquid phase. In a preferred embodiment, the particulate material comprises the dye transfer inhibitor PVNO (see above for a detailed description), aluminosilicate detergent builders and other particulate subcomponents.

(A) Bleach and Optional Bleach Activator- The most preferred type of particulate material useful in the present detergent compositions are particles of peroxygen bleach. Such peroxygen bleaches can be organic or inorganic in type. Inorganic peroxygen bleaches are often used in combination with bleach activators.

Useful organic peroxygen bleaches include percarboxylic acid bleaches and salts thereof. Suitable examples of this type of agent are magnesium monoperoxyphthalate hexahydrate, the magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxidedecanedioic acid. 19 such bleach
Hartman US Pat. No. 4,483,781, issued Nov. 20, 1984, 1
European patent application EP-A-133, Banks et al., Published February 20, 985.
354, and Chung et al., US Pat. No. 4,4, issued Nov. 1, 1983.
12, 934. Highly preferred bleaches include January 6, 1987.
6 as described in US Pat. No. 4,634,551 to Burns et al.
There is also -nonylamino-6-oxoperoxycaproic acid (NAPAA).

Inorganic peroxygen bleaches may also be used in particulate form in the detergent composition. Inorganic bleaches are practically preferred. Such inorganic peroxygen compounds include alkali metal perborates and percarbonate materials, most preferably percarbonates. For example, sodium perborate (eg, mono- or tetrahydrate) is used. Suitable inorganic bleaches also include sodium or potassium carbonate peroxyhydrate and the corresponding "percarbonate" bleach, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (eg, OXONE from DuPont) may also be used. Inorganic peroxygen bleach is often coated with silicates, borates, sulphates 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 bleaching agents, such as perborate, percarbonate, etc., are preferably combined with a bleach activator, which corresponds to the bleach activator in the aqueous solution (ie in the case of fabric washing / bleaching). Are generated in situ (during use of the composition). Various non-limiting examples of activators include US Pat. No. 4,915,85 issued to Mao et al. On Apr. 10, 1990.
4 and Chung et al., US Pat. No. 4,412, issued Nov. 1, 1983.
934. Nonanoyloxybenzene sulfonate (NOBS)
And tetraacetylethylenediamine (TAED) activator is typical. Mixtures thereof may also be used. See also US Pat. No. 4,634,551, supra, for other exemplary bleaches and activators useful herein.

Another useful amide-derived bleach activator is An.
US Pat. No. 5,891,838 issued to Gell et al. and 60 / 088,170 filed June 5, 1998, P & G Case No. 7173P, entitled "Non-Aqueous Liquid Detergent Composition Containing Gasified Particulate Matter," in Diane Parry's co-pending provisional application, both incorporated herein by reference.

If peroxygen bleaches are used as all or part of the added particulate material, they are typically about 1-30% by weight of the composition. More preferably, the peroxygen bleach is about 1-20% by weight of the composition. Most preferably, the peroxygen bleach is present to the extent of about 5-20% by weight of the composition. If used,
The bleach activator is about 0.5-20% by weight of the composition, more preferably about 3%.
-10%. In many cases, the molar ratio of bleach to activator is about 1: 1 to 1
The activator is used so that it is 0: 1, more preferably about 1.5: 1 to 5: 1.

(B) Transition Metal Bleach Catalysts- Another possible type of additive particulate material that may be suspended in the present liquid detergent compositions is a transition metal bleach catalyst that promotes catalytic oxidation of soil and stains on the fabric surface. . Such compounds, in catalytically effective amounts, preferably from about 1 ppb to about 99.9% of the laundry detergent composition, more typically from about 0.001 to about 49.
%, Preferably about 0.05 to about 500 ppm (“ppb” stands for parts per billion by weight and “ppm” stands for parts per million by weight). The transition metal bleach catalyst is coordinated with a macropolycyclic rigid ligand, preferably a bridged macropolycyclic ligand, having at least 4 donor atoms, at least 2 of which are bridgehead donor atoms. , 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 (V), W (VI), Pd (II), Ru (II), Ru (III) and Ru (IV)
Consisting of a transition metal complex selected from the group consisting of). These catalysts are described in P & G Case No. 5, incorporated herein by reference. 6524P, 60/040, 62
Further details are given in the co-pending provisional application of Daryle H. Busch et al.

(C) Organic Builder Materials- Another possible type of additive particulate material that can be suspended in the liquid detergent composition is calcium or other ions found during the laundry / bleaching use of the composition. It is an organic detergent builder substance that acts to counteract the effects of water hardness. Examples of such substances are alkali metals, citrates, succinates, malonates, fatty acids, carboxymethylsuccinates, carboxylates, polycarboxylates and polyacetylcarboxylates. Specific examples are the sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid and citric acid. Other examples are alkane hydroxyphosphonates and organic phosphonate type sequestrants such as those sold by Monsanto under the trade name Dequest. Citrate salts are highly preferred.

Other suitable organic builders include high molecular weight polymers and copolymers known to have builder properties. For example, such materials include suitable polyacrylic acids, polymaleic acids, polyacrylic acid / polymaleic acid copolymers and salts thereof, such as BASF having a molecular weight of about 5000 to 100,000.
Are sold under the trade name Sokalan.

Another suitable type of organic builder consists of water-soluble salts of higher fatty acids, or “soaps”. These include from about 8 to about 24 carbon atoms, preferably from about 12 to about 1.
There are alkyl metal soaps such as sodium, potassium, ammonium and alkylol ammonium salts of higher fatty acids having 8 carbon atoms. Soaps are made by direct saponification of fats or oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of a mixture of fatty acids derived from coconut oil and tallow, ie sodium or potassium tallow and coconut soap.

If utilized as all or part of the added particulate material, the insoluble organic detergent builder is typically about 2-20% by weight of the composition. More preferably, such builder material is about 4-10% by weight of the composition.

(D) Inorganic Alkaline Source— Another possible type of additive particulate material that can be suspended in the present liquid detergent compositions is to render aqueous cleaning solutions formed from such compositions alkaline in nature. It is a substance that works like. Such materials may or may not act as detergent builders, ie, materials that counteract the adverse effects of water hardness on cleaning performance.

Examples of suitable alkali sources are water-soluble alkali metal carbonates, bicarbonates, borates, silicates and metasilicates. Although not preferred for economic reasons, water-soluble phosphates can also be used as the alkalinity source. These include alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Of all these sources of alkali, alkali metal carbonates such as sodium carbonate are most preferred.

The alkalinity source, if in the form of a hydratable salt, may also act as a desiccant in the present liquid detergent composition. The presence of the alkalinity source, which is also a desiccant, is effective in chemically stabilizing composition components such as peroxygen bleach, which are susceptible to inactivation by water.

If utilized as all or part of the added particulate material component, the alkalinity source is typically about 1 to 25% by weight of the composition. More preferably, the alkalinity source is about 2-15% by weight of the composition. Such materials, although water soluble, are usually insoluble in the present non-aqueous detergent compositions.

As indicated, the present aqueous and non-aqueous liquid detergent compositions contain a surfactant, preferably a structured, preferably solid suspension suspended and dispersed throughout the non-aqueous liquid phase. The phases take the form of bleach and / or other substances in particulate form. Generally, the structured non-aqueous liquid phase is about 49-99.95% by weight of the composition, more preferably about 52-9.
8.5% and the added solids material dispersed is about 1 to 50% by weight of the composition, more preferably about 29 to 44%. Very small amounts of water may be incorporated into the particulate-containing non-aqueous embodiment of the liquid detergent composition. However, in such embodiments, the amount of free water should never exceed about 1% by weight of the composition. More preferably, the water content of the non-aqueous detergent composition is not more than about 1% by weight.

As disclosed herein, the compositions of the present invention may be used to form an aqueous laundry detergent composition. Additional ingredients suitable for use in the aqueous liquid laundry detergent composition are Fr.
edj et al US Patent 5,783,548 and Smerznak et al US Patent 5,648,
Seen at 327. The present particulate-containing non-aqueous liquid detergent composition is relatively viscous and phase stable under the conditions of commercial and use of such compositions. Often, the composition has a viscosity of about 300.
~ 8000 cps, more preferably about 1000-4000 cps. For purposes of this invention, viscosity is measured on a Carrimed CSL2 Rheometer at a shear rate of 20 s ^-1 . The process for making the non-aqueous liquid detergent composition is described in P & G Case No. 09 / 202,964 filed December 23, 1998, incorporated herein by reference. 615
It is described in detail in the co-pending application of Jay I. Kahn et al.

An effective amount of the present liquid detergent composition that is added to water to form an aqueous wash / bleach solution is an amount sufficient to form about 500 to 10,000 ppm of the composition in aqueous solution. More preferably, about 800-8000 ppm of the detergent composition is placed in the wash / bleach solution.

B. Granule / Powder Product The granule / powder detergent product of the present invention comprises, in addition to one or more hydrotropes, preferably one or more of the following preferred ingredients, and optionally one or more conventional detergent additive materials. Become. Such conventional additives include one or more of the solid particulate materials described in the Liquid Products section above or the Conventional Detergent Additives section below.

While it is well known that the use of hydrotropes can provide desirable phase formation and product viscosity, it prevents gelling and / or thickening of the detergent compositions disclosed herein to prevent the formation of granular detergent products. The use of these organic molecules as hydrotropes to improve elution and dispersion performance has not yet been disclosed. Gelation
It has already been observed with detergent products made without a hydrotrope as defined in this invention when the product was first contacted with water and diluted.

Without being bound by theory, this gelation phenomenon occurs when a viscous surfactant phase (typically: It is believed that the surfactant-containing particles form lamella, spherulitic or hexagonal phases) or internally bound "lump-gels". There is a correlation between the viscosity of the product-water mixture in the critical dilution range where gelation is observed and the amount of viscous surfactant phase formed in this range. The problem is particularly noticeable in areas where washing of fabrics by an automatic clothes washing machine is performed under relatively cold wash water or mild agitation (for example, Japan). In a typical surfactant-water phase diagram, relatively cold wash water temperatures produce a stable portion for the highly viscous neat or gel surfactant phase. Under mild stirring conditions, the mechanical energy applied by the stirrer is insufficient to destroy the formation of these highly viscous phases.

The granular detergent compositions disclosed herein may be in the form of single particles or multiparticulates, each having its own composition. When the detergent is composed of a multiplicity of detergent particles, the organic hydrotrope described above is preferably contained in or coated on the surface of the surfactant-rich particles.

Preferred Ingredients Detergent Surfactants- Anionic surfactants useful in the present invention may be formed in either particle with an alkyl sulphate surfactant which is separated from the electrolyte in the detergent composition according to the present invention. Good residual anionic surfactant. For the purposes of the present invention, alkyl sulphates are alkyl sulphates, alkyl alkoxy sulphates, alkyl sulphonates, alkyl alkoxy carboxylates,
Defined as an alkylalkoxylated sulphate, the remaining anionic surfactants are selected from the group consisting of alkylbenzene sulphonates, α-olefin sulphonates, paraffin sulphonates, alkyl ester sulphonates, sarcosinates, taurinates and mixtures thereof.

When present, the anionic surfactant is typically present in the total detergent composition in an effective amount. More preferably, the composition may contain an anionic surfactant in at least about 0.5% by weight of the composition, more preferably at least about 5%, even more preferably at least about 10%. The composition may preferably contain no more than about 90% by weight of the composition, more preferably no more than about 50%, and even more preferably no more than about 30% with an anionic surfactant.

[0067]   It provides excellent overall cleaning performance by itself, especially polyhydroxy fatty acid
Full range of temperatures, wash concentrations and wash times when used with Mido (see below)
Delivers good fat / oil cleaning properties over
Alkyl monkeys that provide a solution, yet provide improved formulatability in liquid detergent formulations
Fate surfactants have the formula ROSO_ThreeA water-soluble salt or acid of M (R is preferably C ₁₀ -C₂₄Hydrocarbyl, preferably C₁₀-C₂₀Having an alkyl moiety
Alkyl or hydroxyalkyl, more preferably C₁₂-C₁₈Alkyl
Or hydroxyalkyl, M is H or a cation, for example alkali (IA
Group) metal cations (eg sodium, potassium, lithium), substituted or non-
Substituted ammonium cations such as methyl-, dimethyl- and trimethylan
Monium, and quaternary ammonium cations such as tetramethylammonium
And dimethylpiperidinium cation, and ethanolamine, dietano
Derivates derived from alkanolamines such as ruamine and triethanolamine.
Thione, and mixtures thereof. Typically C_12-16Alkyl chain of
Is preferred at low wash temperatures (eg below about 50 ° C.), and C_16-18Alkyl chain
Higher wash temperatures (eg about 50 ° C. or higher) are preferred.

Another suitable type of alkyl sulphate surfactant according to the invention is
It is a secondary (2,3) alkyl sulfate. These surfactants are preferably of the formula:

[Chemical 11] In the above formula, x and (y + 1) are integers of at least about 7, preferably at least about 9. Preferably, these surfactants have 10 to 18 carbon atoms.
Suitable examples of these anionic surfactants are Mo, published February 8, 1966.
rris US 3,234,258, Lutz US 5,075,041 issued December 24, 1991, Lutz et al US 5 issued September 20, 1994.
, 349, 101 and US 5, 5 of Prieto published February 14, 1995.
389,277, each of which is incorporated herein by reference.

Another suitable type of alkyl sulphate surfactant according to the invention is
It is an alkylalkoxylated sulfate. These surfactants are typically water-soluble salts or acids of the formula RO (A) _m SO ₃ M, where R is an unsubstituted C ₁₀ -C ₂₄ alkyl or C ₁₀ -C ₂₄ alkyl moiety. Has a hydroxyalkyl group, preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically Is about 0.5 to about 6
, More preferably about 0.5 to about 3, and M is H or a cation, such as a metal cation (eg, sodium, potassium, lithium, etc.), ammonium or a substituted ammonium cation. Alkyl ethoxylated sulphates and alkyl propoxylated sulphates are considered here. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethyl-ammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. There are cations derived from, and mixtures thereof. Examples of the surfactant include C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate (2.25) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate ( 3.0) Sulfate and C ₁₂ -C ₁₈ alkyl polyethoxylates (
4.0) sulphate, where M is conveniently selected from sodium and potassium. Surfactants useful herein may be prepared from natural or synthetic alcohol sources. Chain length represents the average hydrocarbon distribution including branches. The anionic surfactant component, conventional alcohol sources, such as natural alcohols, synthetic alcohols, e.g. ^{NEODOL TM, ALFOL TM, LIAL TM} , alkyl sulfates derived from those sold under the trade names such as LUTENSOL ^TM And there are also alkyl ether sulphates. Alkyl ether sulphates are also known as alkyl polyethoxylate sulphates.

Another type of alkyl sulphate surfactant according to the invention is one or more (preferably a mixture of two or more) medium chain branched surfactants, preferably medium chain branched alkylalkoxy alcohols having the formula: :

[Chemical 12] Medium chain branched alkyl sulphate having the formula:

[Chemical 13] And a medium chain branched alkylalkoxysulfate having the formula:

[Chemical 14] Where, in the above, the total number of carbon atoms in the branched primary alkyl moiety of these formulas is
Number (R, R¹And R^TwoCharcoal with branching but with EO / PO alkoxy moiety
(Not including elementary atoms) is 14 to 20; and in the case of this surfactant mixture,
The average total number of carbon atoms in the branched primary alkyl moiety having the above formula is 14.5.
Greater than about 17.5 (preferably about 15 to about 17); R, R ¹ And R^TwoAre each independently hydrogen, C₁-C_ThreeAlkyl and their mixtures
Selected from, preferably methyl; provided that R, R¹And R^TwoIs all hydrogen
Never, when z is 1, at least R or R¹Is not hydrogen. M
Is a water-soluble cation, and two or more types of cations, such as sodium and cations.
It may be a mixture of helium. Index w is an integer from 0 to 13; x is
Y is an integer of 0 to 13; y is an integer of 0 to 13; z is an integer of at least 1.
However, w + x + y + z is 8 to 14. EO and PO have the following formula
Represents a tyleneoxy unit and a propyleneoxy unit, respectively:

[Chemical 15] However, other alkoxy units, especially 1,3-propyleneoxy, butoxy and mixtures thereof, are also suitable as alkoxy units attached to the mid-chain branched alkyl moiety.

The mid-chain branched surfactant is preferably a mixture of surfactant systems. Thus, when the surfactant system comprises an alkoxylated surfactant, the index m indicates the average degree of alkoxylation within the mixture of surfactants. in this way,
The index m is at least about 0.01, preferably about 0.1, more preferably about 0.5, most preferably about 1 to about 30, preferably about 10, more preferably about 5.
Within the range of. When considering a medium chain branched surfactant system containing only alkoxylated surfactants, the value of the index m represents the distribution of the average degree of alkoxylation corresponding to m, or it is exactly the number of units corresponding to m. It may also be a single specific chain which is alkoxylated (eg ethoxylated and / or propoxylated).

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

[Chemical 16] Or the following formula:

[Chemical 17] Wherein a, b, d and e are a + b of 10 to 16 and d + e
Is an integer such that is 8 to 14; M is selected from sodium, potassium, magnesium, ammonium and substituted ammonium, and mixtures thereof.

The surfactant system of the present invention comprising a mid-chain branched surfactant is preferably formulated in two aspects. A first preferred embodiment comprises a mid-chain branched surfactant formed from a feedstock containing no more than 25% mid-chain branched alkyl units. Thus, prior to mixing with any other conventional surfactant, the mid-chain branched surfactant component contains up to 25% of surfactant molecules that are non-linear surfactants. A second preferred embodiment comprises a mid-chain branched surfactant formed from a feedstock containing about 25 to about 70% mid-chain branched alkyl units. Thus, prior to mixing with any other conventional surfactant, the mid-chain branched surfactant component contains from about 25 to about 70% surfactant molecules that are non-linear surfactants. ..

These surfactants are described in US patent application 60/0606 dated October 14, 1997.
No. 1,971, Agent Case No. 6881P; 60 / of October 14, 1997
061,975, Agent Case No. 6882P; 6 of October 14, 1997
0 / 062,086, Agent Case No. 6883P; 60 / 061,916, October 14, 1997, Agent Case No. 6884P; October 14, 1997
60 / 061,970 of the date, Agent Case No. 6885P; 60 / 062,407, October 14, 1997, Agent Case No. Further described in 6886P. Other suitable mid-chain branched surfactants are described in US patent application 60 / 032,03.
5 (Case 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. 6406P) and 60 / 031,844 (Case No. 6409P). Mixtures of these branched surface-active agents with conventional linear surface-active agents are also suitable for use in the composition.

Among the anionic surfactants according to the invention which are not included in the alkyl sulphates according to the invention, one type of anionic surfactant which can be used is the alkyl ester sulphonates. Because they can be produced from renewable non-petroleum sources,
These are desirable. The alkyl ester sulfonate surfactant component can be produced according to known methods disclosed in the technical literature. For example, linear esters of C ₈ -C ₂₀ carboxylic acids are described in "The Journal of the American Oil Chemists Society", 52 (19).
75), pp. 323-329, and can be sulfonated with gaseous SO ₃ . Suitable starting materials include natural fatty materials such as those derived from tallow, palm and coconut oil.

Particularly preferred alkyl ester sulfonate surfactants for laundry applications include:
There are alkyl ester sulfonate surfactants of the structural formula:

[Chemical 18] In the above formula, R ³ is C ₈ -C ₂₀ hydrocarbyl, preferably alkyl, or a combination thereof, R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl, or a combination thereof, and M is a water-soluble salt. It is a forming cation. Suitable salts include
Metal salts such as sodium, potassium and lithium salts, substituted or unsubstituted ammonium salts such as methyl-, dimethyl-, trimethyl- and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium,
And cations derived from alkanolamines, such as monoethanolamine, diethanolamine and triethanolamine. Preferably R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Methyl ester sulfonates in which R ³ is C ₁₀ -C ₁₆ alkyl are particularly preferred.

[0077]   Another type of anionic surfactant that can be used is alkylbenzes.
Sulfonate. These include various HFs or solid HFs such as DETAL
^RManufactured by known processes such as (UOP) process or other Lewis
Acid catalyst, eg AlCl_ThreeManufactured with or using acidic silica / alumina
Also known as LAS, produced by or manufactured from chlorinated hydrocarbons
Hard (ABS, TPBS), linear type, eg C₉-C₂₀Straight chain alk
Rubenzenesulfonate, especially sodium linear alkyl C₁₀-C₁₅benzene
There is a sulfonate. These surfactants are typically of the formula RASO_ThreeWater soluble in M
Salt or acid, where R is branched or straight chain C₁₀-C₂₄Alkyl group, good
More preferably C₁₀-C₂₀Alkyl, more preferably C₁₀-C₁₈In alkyl
A is an aryl group, preferably benzene or toluene, more preferably benzene.
Is a zen unit, M is H or a cation, such as a metal cation (eg, sodium
, Potassium, lithium, etc.), ammonium or substituted ammonium cations
is there.

The surfactant system of the laundry detergent composition of the present invention comprises about 0.001% by weight of the surfactant system, preferably about 1%, more preferably about 5%, most preferably about 10% to about. 1
00%, preferably about 60%, more preferably about 30% of one or more (preferably a mixture of two or more) modified alkylaryl sulfonate surfactants, ie ML.
AS, preferably a surfactant in which the aryl unit is a benzene ring having the formula: may also be included:

[Chemical 19] Where L is an acyclic hydrocarbyl moiety having 6 to 18 carbon atoms; R ¹ , R^TwoAnd R^ThreeAre each independently hydrogen or C₁-C_ThreeAlkyl, but
R¹And R^TwoIs not attached to the end of the L unit; M is water-soluble with a charge q
Are cationic cations, a and b are selected together to satisfy charge neutrality.

These and other suitable MLAS surfactants are described in co-pending US patent application 60 / 053,319, filed Jul. 21, 1997, Attorney Case No. 676
6P; filed on July 21, 1997, 60 / 053,318, Agent Case No. 6767P; filed on July 21, 1997 60 / 053,321
, Agent Case No. 6768P; filed on July 21, 1997 60/0
53, 209, Agent Case No. 6769P; 60 / 053,328, filed July 21, 1997, Agent Case No. 6770P; July 21, 1997
60 / 053,186 filed on date, Agent Case No. 6771P; 199
60 / 105,017 filed on October 20, 1998, Agent Case No. 73
03P; 60 / 104,962, filed October 20, 1998, Agent Case No. 7304P; filed on October 20, 1998 60/104,
962, Agent Case No. 7304P; and 60 / 144,519 filed Jul. 19, 1999, Agent Case No. Further described in 7663P. Mixtures of these modified surfactants with conventional and / or branched surfactants, such as those described herein, are also suitable for use in the composition.

Examples of suitable anionic surfactants are “Surface Active Agents and Detergent”.
s "(Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants have been described in US published by Laughlin et al. on Dec. 30, 1975.
It is also generally disclosed in Patent 3,929,678 at column 23, line 58 to column 29, line 23.

[0081]   Other anionic surfactants useful for cleaning purposes may also be included in the composition.
. These include soap salts (eg sodium, potassium, ammonium and
Substituted ammonium salts, including mono, di and triethanolamine salts),
C₈-C₂₂Primary or secondary alkane sulfonate, C₈-C₂₄Olefins
Ruphonates, for example as described in British Patent Specification No. 1,082,179
Sulfur produced by sulfonation of the thermal decomposition products of alkaline earth metal citrates.
Phonated polycarboxylic acid, alkyl glycerol sulfonate, fatty acyl glyce
Roll sulfonate, fatty oleyl glycerol sulfate, alkyl pheno
Ethylene oxide ether sulfate, paraffin sulfonate, alk
Ruphosphate, isethionates such as acyl isethionates, N-acyltates
Urate, fatty acid amide of methyl tauride, alkylsuccinamate and sulphate
Monoesters of fosuccinate, sulfosuccinate (especially saturated and unsaturated C ₁₂ -C₁₈Monoesters), diesters of sulfosuccinates (especially saturated and
And unsaturated C₆-C₁₄Diester), N-acyl sarcosinate, alkyl poly
Alkyl polysaccharide sulfates such as glucoside sulfates (nonionic non-
Sulfate compounds are described below), branched primary alkyl sulphates
, The formula RO (CH_TwoCH_TwoO)_kCH_TwoCOO⁻M⁺(R is C₈-C₂₂Alkyl
And k is an integer from 1 to 10 and M is a soluble salt-forming cation).
Alkyl polyethoxycarboxylate, esterified with isethionic acid to give water
Some fatty acids are neutralized with sodium oxide. Present in tall oil or
Derived from it, such as rosin, hydrogenated rosin, resin acids and hydrogenated resin acids
Resin acids and hydrogenated resin acids are also suitable. Another example is "Surface Active Agents  and Detergents "(Vol. I and II by Schwartz, Perry and Berch)
It A variety of such surfactants have been described by Laughlin et al. On Dec. 30, 1975.
Column 23 line 58 to column 29 line 23 of issued US Pat. No. 3,929,678
However, it is generally disclosed.

Another type of useful anionic surfactant is the so-called dianionic system. These are surfactants in which at least two anionic groups are present in the surfactant molecule. Some suitable dianionic surfactants are all 28 June 1996.
Co-pending USSN 60 / 020,503 (Case No. 6160) filed on date
P), 60 / 020,772 (Case No. 6161P), 60 / 020,928
(Case No. 6158P), 60 / 020,832 (Case No. 6159P) and 60 / 020,773 (Case No. 6162P), and August 8, 1996
Filed 60 / 023,539 (Case No. 6192P), dated 60/02
3,493 (Case No. 6194P), 60 / 023,540 (Case No. 61)
93P) and 60 / 023,527 (Case No. 6195P), the disclosures of which are incorporated herein by reference.

C. Tablet Product The tablet detergent product of the present invention comprises, in addition to one or more hydrotropes (“binders” as they have an adhesive effect in tablets), preferably one or more of the following preferred ingredients, And optionally one or more conventional detergent additive materials.
Such conventional additive materials include one or more of the solid particulate materials described in the liquid product section and / or granule / powder product section above or the conventional detergent additive material section below.

Detergent tablet formulations usually contain at least a small amount of binder in the composition in order to exert an adhesive effect and promote tablet uniting. For the purposes of the present invention, the adhesion effect of the detergent matrix on the particulate material is characterized by the force required to break a tablet based on the test detergent matrix compressed under controlled compression conditions.
A means for assessing tablet strength (also called diametral breaking stress) is the Pharmaceutic
al dosage forms: tablets, volume 1, Ed.HALieberman et al, published in 19
Seen at 89.

The addition of these hydrotropes to the particulate material produced according to the invention has an adhesive effect when it is compressed into a tablet and formed into tablets, while also exhibiting excellent disintegration performance in wash water. I understood. The detergent tablets containing this hydrotrope have high tensile strength at constant compression force or comparable tensile strength at lower compression force when compared to traditional tablets.

In addition to the adhesive effect they exert, these hydrotropes are important ingredients in preventing gelation and / or thickening of the detergent compositions disclosed herein.
Gelation was already observed in detergent products made without a hydrotrope as defined in this invention when the product was first contacted with water and diluted. Without being bound by theory, this gelation phenomenon occurs when the surfactant is in a viscous surfactant phase (typically lamellae, spherulitic or It is considered that this is because the surfactant-containing particles form a hexagonal phase). There is a correlation between the viscosity of the product-water mixture in the critical dilution range where gelation is observed and the amount of viscous surfactant phase formed in this range. Without being bound by theory, hydrotropes effectively interact with the ordered layers of surfactant molecules, destroying them and promoting the formation of an isotropic low viscosity surfactant phase, It is believed that the above hydrotropes prevent the formation of a viscous surfactant phase that forms upon dilution.

In the present invention, there is also the additional effect that the inclusion of these particular hydrotropes extends the "operating window" of the detergent tablet. Operating window refers to the bulk density range of detergent tablets as they are produced on an industrial scale. Due to several variables, the detergent tablet densities deviate somewhat from the ideal or preferred densities during industrial scale manufacture of detergent tablets. The operating window is the range of densities that a tablet is not, but still acceptable, to consider acceptable. Below the operating window, the density is too low as a result of insufficient packing and sticking during the compression step, so that the tablets are very brittle and fragile during handling and storage. Above the operating window, the tablets are too tightly packed and are likely to be poorly dissolved and dispersed in the wash liquor during the wash process.

In addition to these hydrotropes mentioned above, the detergent tablets may also contain additional non-gelling binders. The non-gelling binder not only has an adhesive effect, but also promotes elution. When a non-gelling binder is used, suitable non-gelling binders include synthetic organic polymers such as polyethylene glycol, polyvinylpyrrolidone, polyacrylates and water soluble acrylate copolymers. Handbook of Pharmaceutical E
The xcipients, second edition has the following binder classifications: gum arabic, alginic acid, carbomer, sodium carboxymethyl cellulose, dextrin, ethyl cellulose, gelatin, guar gum, hydrogenated vegetable oil type I, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, liquid. glucose,
Aluminum magnesium silicate, maltodextrin, methyl cellulose, polymethacrylate, povidone, sodium alginate, starch and zein.
Most preferred binders, such as cationic polymers, ie ethoxylated hexamethylenediamine quaternary compounds, bishexamethylenetriamine or others, such as pentaamines, ethoxylated polyethyleneamines, maleic acid acrylic polymers, also have an active cleaning function in laundry washing. Have

Since the non-gelling binder material is preferably sprayed, a suitable temperature below 90 ° C., preferably below 70 ° C., even more preferably below 50 ° C., so as not to damage or decompose other active ingredients in the matrix. It has a high melting point. Most preferred is
A non-aqueous liquid binder (ie not an aqueous solution) that is sprayed in the molten state.
However, they should be binding within the tablet, although they may be solid binders which are incorporated into the matrix by dry addition. Detergent tablets made in accordance with the present invention comprise an essential hydrotrope separated from each other by at least 5, preferably 6 aliphatic carbon atoms by two polar groups, from about 0.05 to about.
About 5% by weight, preferably about 0.1 to about 3%, most preferably about 0.1 to about 1%. When any non-gelling binder material is used and they are present in the detergent tablet, they are about 0.1 to about 7% of the detergent tablet, preferably about 0.5 to about 5%,
More preferably, it is used at a level of about 1 to about 3%. When any non-gelling binder is used, they are about 2: 1 to about 60: 1, preferably about 3: 1 to about 30 :.
It is present in the detergent tablet in a ratio of 1, more preferably about 3: 1 to about 15: 1 non-gelling binder to specific hydrotrope binder.

Disintegrants- It is necessary that the tablets have good integrity before use, but they should also disintegrate quickly when in contact with wash water during use. for that reason,
It is also known to include a disintegrant that promotes tablet disintegration. Various types of disintegrants are known, including those in which disintegration occurs due to swelling of the disintegrant. Various swellable disintegrants have been presented in the literature, with starch, cellulose and water-soluble organic polymers being the main preference. Inorganic swellable disintegrants such as bentonite clay are also mentioned, for example in EP-A-466,484. Some substances act as binders and disintegrants. It is also described therein that the disintegrant exhibits complementary building, anti-redeposition or fabric softness. The amount of disintegrant is preferably 1-5%. A tablet may have multiple discrete areas, such as layers,
EP- may have a heterogeneous structure containing inserts or coatings
Proposed in A-466,484.

Tablet Making- The detergent tablets of the present invention are prepared by mixing the solid ingredients together and compressing the mixture in a conventional tablet press such as is used in the pharmaceutical industry.
Easy to manufacture. Preferably, the main component, especially the gelling surfactant, is used in particulate form. Any liquid component, such as surfactants or suds suppressors, may be incorporated into the solid particulate component in the conventional manner. Ingredients such as builders and surfactants may be spray dried by conventional methods and then compressed under suitable pressure. Preferably, the tablets according to the invention are compressed using a force of 100,000 N or less, more preferably 50000 N or less, even more preferably 5000 N or less, most preferably 3000 N or less. In practice, the most preferred embodiment is a tablet compressed using a force of 2500 N or less.

The particulate material used to make the tablets of the invention may be prepared by any granulation or granulation process. An example of such a process is spray drying (in a co-current or counter-current spray drying tower), which typically results in low bulk densities of 600 g / L or less. Higher density particulate material may be granulated and densified in a high shear batch mixer / granulator, or (eg, Lodi
ge ^R CB and / or Lodige ^R KM mixer) continuous granulation and densification processes. Other suitable processes include fluidized bed processes, compression processes (eg roll compaction), extrusion, as well as chemical processes such as agglomeration, crystallization centering, etc., where particulate matter is made. The individual particles may be any other particles, granules, spheres or granules.

The ingredients of the particulate material may be mixed together by any conventional means. Batch is
For example, a concrete mixer, Nauta mixer, ribbon mixer or any other is suitable. Alternatively, the mixing process may be carried out continuously by weighing each component onto a moving belt and blending them in one or more drums or mixers. Non-gelling binders may also be sprayed onto the mixture of some or all of the components of the particulate material. Other liquid ingredients may also be sprayed or premixed separately into the mixture of ingredients. For example, a slurry of perfume and optical brightener may be sprayed. Microfluidic aids (powder such as zeolites, carbonates, silicas) can also be added to the particulate material after spraying the binder, preferably towards the end of the process, to make the mixture less sticky.

Tablets may be manufactured using any compression process, such as tableting, briquetting or extrusion, preferably tableting. Suitable devices include standard single stroke or rotary presses (eg Courtoy ^R , Korch ^R , Manesty ^R or Bonals ^R ). The tablets produced according to the invention are preferably 20-6.
Diameter of 0 mm, preferably at least 35 mm to 55 mm, and 15-1
It has a weight of 00 g. The height to diameter (or width) ratio of the tablets is preferably 1: 3 or more, more preferably 1: 2 or more. The compression force used to produce these tablets does not exceed 100,000 kN / m ² , preferably 30,000 kN / m ^2.
m ^{2 or} less, more preferably 5000 kN / m ^{2 or} less, even more preferably 30
Not exceed 00kN / m ^2, and most preferably not exceed a 1000 kN / m ^2. In a preferred embodiment according to the invention the tablet is at least 0.9 g / cc, more preferably at least 1.0 g / cc, preferably less than 2.0 g / cc, more preferably less than 1.5 g / cc and even more. It preferably has a density of less than 1.25 g / cc, most preferably less than 1.1 g / cc. Multilayer tablets may be manufactured by known techniques.

Coating- The solidity of the tablets according to the invention may be further improved by producing coated tablets, the coating covering uncoated tablets according to the invention while further improving the mechanical properties of the tablets. , Maintain or further improve dispersibility.

In one aspect of the invention, the tablets may be coated such that the tablets do not absorb water or absorb water at a very slow rate. The coating is handled,
It may be strong enough to undergo very low levels of breakage or damage, even for moderate mechanical shocks that the tablet receives during packaging and shipping. Finally, the coating is preferably brittle enough that the tablet breaks when subjected to higher mechanical shocks. Furthermore, it is advantageous if the coating material is dispersed under alkaline conditions or easily emulsified with a surfactant. This also helps to avoid the visible residue residue in the windows of the front-loading washing machine during the wash cycle, and also to avoid the deposition of particles or clumps of coating material on the laundry. Water solubility is “Standard Test Method for Measurements of Aqueous Solubilit
It is measured according to the ASTM E1148-87 test protocol entitled "y".

A suitable coating material is a dicarboxylic acid. A particularly suitable dicarboxylic acid is
It is 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, dodecanedioic acid, tridecanedioic acid and mixtures thereof. The coating material preferably has a melting point of 40-200 ° C.

The coating can be applied in several ways. Two preferred coating methods are a) coating with a molten substance and b) coating with a solution of that substance. In a), the coating material is applied at a temperature above its melting point and solidifies on the tablets. In b) the coating is applied as a solution and the solvent is dried so as to leave an adherent coating. The substantially insoluble substance may be applied to the tablets, for example by spraying or dipping. Usually, when the molten substance is sprayed onto the tablets,
Rapidly solidifies to form an adherent coating. Rapid cooling also results in rapid solidification of the coating material when the tablets are dipped into the molten material and then removed. It has been found that apparently substantially insoluble substances with melting points below 40 ° C. are not completely solid at ambient temperature, and substances with melting points above about 200 ° C. are impractical. Preferably, the material melts in the range 60-160 ° C, more preferably 70-120 ° C. "Melting point" means the temperature at which a substance becomes a clear liquid when heated slowly, for example in a capillary tube.

Coatings of any desired thickness may be applied according to the present invention. For most purposes, the coating is 1-10% of the tablet weight, preferably 1.5-5%. The tablet coating is preferably very stiff and provides additional strength to the tablet.

In a preferred embodiment of the invention, the destructiveness of the coating upon cleaning is improved by adding a disintegrant to the coating. This disintegrant swells once in contact with water and then breaks the coating into smaller parts. This also improves the dispersibility of the coating in the wash liquor. The disintegrant is within 30% by weight, preferably 5
Suspended in the molten coating at a level of -20%, most preferably 5-10%. Possible disintegrants are described in the Handbook of Pharmaceutical Excipients (1986). Examples of suitable disintegrants are starch: natural, modified or pregelatinized starch, sodium starch gluconate; gums: agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum; croscarmylose sodium, crospovidone. , Cellulose, carboxymethylcellulose, alginic acid and its salts, such as sodium alginate, silicon dioxide,
There are clays, polyvinylpyrrolidone, soybean polysaccharides, ion exchange resins, and mixtures thereof.

Tensile Strength- Depending on the composition of the starting materials and the shape of the tablets, the compression force used is adjusted so as not to influence the tensile strength and the disintegration time in the washing machine. This process may be used to produce uniform or laminated tablets of any size or shape.

In the case of a cylindrical tablet, the tensile strength corresponds to the diameter breaking stress (DFS), which is a method for expressing the strength of the tablet and is defined by the following formula: = 2F / πDt F is the maximum force (Newton) that causes tensile failure (breaking), and Van Ke
measured by VK200 Tablet Hardness Tester supplied by ll industries, Inc. D is the diameter of the tablet and t is the thickness of the tablet (Method Pharmaceutical Dosage For
ms: Tablets, Volume 2, Page 213-217). A diametral breaking stress of at least 25 kPa is preferred.

This also applies to non-cylindrical tablets in defining tensile strength, the cross section perpendicular to the tablet height is not circular, the force is perpendicular to the tablet height direction and Applied in a direction perpendicular to the sides of the, the sides being perpendicular to the non-circular cross section.

Optional Conventional Detergent Additives In addition to the ingredients of the composition of the present invention described above, the detergent composition can, and preferably will, include various other optional ingredients.

(A) Inorganic Detergent Builder -The detergent composition may optionally contain one or more types of inorganic detergent builders in addition to those listed above that also function as an alkalinity source. Such optional inorganic builders include aluminosilicates such as zeolites. Aluminosilicate zeolites and their use as detergent builders are described by Corkill et al. US Pat. No. 4,605,5 issued Aug. 12, 1986.
09, the disclosure of which is incorporated herein by reference.
Crystalline laminated silicates such as those described in the '509 US Patent are also suitable for use in the detergent composition. If utilized, the optional inorganic detergent builder is about 2-15% by weight of the composition.

(B) Enzymes -Enzymes are present in the formulation for a variety of fabric laundering purposes, including protein-based, carbohydrate-based or triglyceride-based stain removal, free dye transfer prevention, and fabric regeneration. May be included. It is believed that the addition of the particular hydrotrope described above enhances enzyme performance in detergent compositions. This is because as the hydrotrope increases the rate of dissolution of the detergent composition, the rate at which the enzyme is contacted with water and activated is increased, and so is the corresponding cleaning effect provided by the activated enzyme. This behavior is found in both aqueous and non-aqueous detergent compositions.

Enzymes that can be added include protease, amylase, lipase, mannanase,
There are cellulases, peroxidases and mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. However, their choice is dictated by several factors, such as pH activity and / or optimal stability, heat stability, and stability to active detergents, builders and the like. In this respect,
Bacterial or fungal enzymes such as bacterial amylases and proteases and fungal cellulases are preferred.

The enzyme is within about 5 mg by weight per gram of composition, more typically from about 0.01 to about.
It is usually formulated at a level sufficient to provide about 3 mg of active enzyme. In other words, the composition is typically about 0.001 to about 5% by weight, preferably 0.01-1.
Contains 0% commercial enzyme product. Protease enzyme is 0.005 per gram of composition
It is usually present in such products at levels sufficient to provide .about.0.1 Anson units (AU) of activity.

Suitable examples of proteases are Bacillus subtilis and Bacillus licheniforms
Is a subtilisin obtained from a specific strain of. Another suitable protease is Ba
obtained from a strain of cillus, having maximum activity in the pH range of 8-12, Novo Industrie
s Developed by A / S and sold under the registered trade name ESPERASE ^R. This enzyme and a method for producing the similar enzyme are described in Novo Industries A / S British Patent Specification No. 1,243,7.
No. 84. MAXATASE commercially available, the proteolytic enzymes suitable for removing protein-based stains, Novo Industries A / S (Denmark) tradename from ALCALASE ^R and ^{SAVINASE R, International Bio-Synthetics,} Inc. From (Netherlands) Some are sold at ^R. Other proteases include
Protease A (European patent application 130,75 published Jan. 9, 1985)
6) and Protease B (see European patent application 87303761.8, filed April 28, 1987 and European patent application 130,756, published on January 9, 1985).

Amylases include, for example, British Patent Specification No. 1,296,839 (Novo Ind
austase A / S), RAPIDASE ^R , International Bio-Synth
etics, Inc., and TERMAMYL ^R, there is a Novo Industries.

The mannanase includes three types of mannan degrading enzymes: EC3.2.1.25: β-mannosidase, EC3.2.1.78: endo-1,4-β-mannosidase (hereinafter referred to as “mannanase”). ), EC 3.2.1.100: 1,4-β-mannobiosidase (I
UPAC Classification-Enzyme nomenclature, 1992, ISBN 0-12-227165-3, Acad
emic Press) is available.

More preferably, the detergent composition of the present invention comprises a β-1,4 called mannanase.
-Comprising mannosidase (EC 3.2.1.78). The term "mannanase" or "galactomannanase" is publicly referred to as mannan endo-1,4-β-mannosidase, which has the alternative names β-mannanase and endo-1,4-mannanase, : Mannan, galactomannan, glucomannan, and mannanase enzymes defined in the art to catalyze the random hydrolysis of 1,4-β-D-mannoside bonds in galactoglucomannan. In particular, mannanases (EC 3.2.1.78) constitute a group of polysaccharases that degrade mannans and are capable of cleaving polyose chains containing mannose units, namely mannan, glucomannan, galactomannan and galactoglucomannan. Represents an enzyme capable of cleaving the glycoside bond of. Mannan is β
Is a polysaccharide having a backbone composed of -1,4-linked mannose, glucomannan is a polysaccharide having β-1,4-linked mannose and glucose alternating in the backbone or more or less regularly, Galactomannans and galactoglucomannans are mannans and glucomannans with α-1,6-linked galactose side chains. These compounds may be acetylated.

The cellulase enzyme used in the detergent composition is preferably formulated at a level sufficient to provide no more than about 5 mg, and more preferably about 0.01 to about 3 mg of active enzyme by weight of composition. It In other words, the composition is preferably about 0.00
1 to about 5% by weight, preferably 0.01 to 1% commercial enzyme product. Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they have an optimum pH of 5-9.5. A suitable cellulase is March 6, 1984.
Dating disclosed in US Pat. No. 4,435,307 to Barbesgoard et al., Where Humic
fungal cellulases from ola insolens or Humicola strain DSM1800 or cellulase 212-producing fungi belonging to the genus Aeromonas and marine molluscs (Dolabella Aur
icula Solander) cellulase extracted from hepatopancreas. Suitable cellulases are GB-A-2,075,028, GB-A-2,095,27.
5 and DE-OS-2,247,832. In addition, cellulases suitable for use herein include WO92-13057 (The Procter & Gamble Compa
ny). Most preferably, the cellulase employed in the detergent compositions herein is commercially available under the product name CAREZYME ^R and CELLUZYME ^R from NOVO Industries A / S.

Suitable lipase enzymes for detergents include those produced by microorganisms of the genus Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154 disclosed in British Patent 1,372,034. See also lipase of Japanese patent application 53/20487, published Feb. 24, 1978. This lipase is trade name Lipase P AMAN
As O ^R Japan, are commercially available from Amano Pharmaceutical Co.Ltd., Nagoya,
This is hereinafter referred to as "Amano-P". Other commercially available lipases include Chromobacter vis
cosum, eg Chromobacter viscosum var.lipol from Toyo Brewery of Takata, Japan
Lipase derived from yticum NRRLB 3673, AMANO-CES ^R ; USA USBiochemical Co
rp. and Chromobacter viscosum lipase from Disoynth Co. of the Netherlands; Pseu
There is a lipase derived from domonas gladioli. Novo derived from Humicola lanuginosa
LIPOLASE ^R enzyme which is commercially available from Industries A / S (see also EPO341,947) is used on a preferred lipase herein.

Peroxidase enzymes are oxygen sources such as percarbonates, perborates,
Used in combination with persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", ie to prevent dyes or pigments that fall off the substrate during the washing operation from transferring to other substrates in the wash liquor. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, by O. Kirk, 1989, 1
It is disclosed in PCT International Application WO 89/09813, published on 19th January and assigned to Novo Industries A / S.

Various enzyme materials, and their means of incorporation into synthetic detergent compositions, are also described in 1971.
It is disclosed in US Pat. No. 3,553,139 issued to McCarty et al. The enzyme is described in US patent 4, to Place et al., Issued July 18, 1978.
Hughes US Patent 4, Issued Mar. 101, 457 and Mar. 26, 1985.
, 507, 219. Enzymatic substances useful in liquid detergent formulations and their incorporation into such formulations is disclosed in US Patent 4,261,868 issued to Hora et al. On April 14, 1981. Enzymes useful in detergents can be stabilized by various techniques. Enzyme stabilization technology dated August 17, 1971
US Patent 3,600,319 issued to Gedge et al., And October 2, 1986.
Venegas European Patent Application Publication 199,405, Application 8620, published on 9th
0586.5 disclosed and exemplified. Enzyme stabilization systems are also described, for example, in US Pat.
, 519, 570. Enzymes added to the composition in the form of conventional enzyme prills are particularly preferred here for use. Such prills are typically about 100 to 1000 microns in size, more preferably about 200 to 800 microns and are suspended in the liquid phase of the composition. Prill in the composition of the present invention,
It has been found in comparison with other enzyme forms that it exhibits particularly desirable enzyme stability with respect to retention of enzyme activity over time. As such, compositions utilizing enzyme prills do not need to include conventional enzyme stabilizers, which often must be used when enzymes are incorporated into aqueous liquid detergents.

(C) Chelating Agents -The detergent composition also optionally contains a chelating agent that acts to chelate metal ions such as iron and / or manganese within the detergent composition. Such chelating agents act to form complexes in the composition with metallic impurities that tend to inactivate composition components, such as peroxygen bleaches. Useful chelating agents include aminocarboxylates, phosphonates, aminophosphonates, polyfunctional substituted aromatic chelating agents and mixtures thereof.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid,
There are ethylenediaminetetrapropionic acid, triethylenetetraaminehexaacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid and ethanoldiglycine. Alkali metal salts of these substances are preferred.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are found in detergent compositions.
ESTs include ethylenediamine tetrakis (methylene phosphonate). Preferably, these aminophosphonates are free of alkyl or alkenyl groups having more than about 6 carbon atoms.

Preferred chelating agents include hydroxyethyldiphosphonic acid (HEDP), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminedisuccinic acid (EDD).
S), dipicolinic acid (DPA) and their salts. Chelating agents can, of course, also act as detergent builders during use of the composition for fabric washing / bleaching. The chelating agent, if used, is about 0.1-4% by weight of the composition.
More preferably, the chelating agent is about 0.2-2% by weight of the detergent composition.

(D) Foam Inhibitors- Foam suppressors may also be particularly important in the present invention due to the high concentration of detergent compositions. The use of suds suppressors in the "High Concentration Cleaning Process" is described in U.S.P.
S. Further details are provided in 4,489,455 and 4,489,574. Various substances are used as suds suppressors, and suds suppressors are well known to those skilled in the art.
For example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Vo
See lume 7, pages 430-447 (John Wiley & Sons, 1979). One category of suds suppressors of particular interest is monocarboxylic fatty acids and their soluble salts. 196
See Wayne St. John, US Pat. No. 2,954,347, issued Sep. 27, 009. The monocarboxylic fatty acids and salts thereof used 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 detergent composition may also contain non-surfactant suds suppressors. These include, for example, high molecular weight hydrocarbons, N-alkylated aminotriazines, monostearyl phosphates, silicone suds suppressors, secondary alcohols (eg 2-alkylalkanols) and mixtures of such alcohols with silicone oils. There is. Hydrocarbon suds suppressors are described, for example, in U of Gandolfo et al., Issued May 5, 1981.
No. 4,265,779. . Silicone suds suppressors are well known in the art, for example Gandolfo et al., US Pat. No. 4,265,779 issued May 5, 1981, and Starch, MS published February 7, 1990.
European patent application 89307851.9. Mixtures of alcohols and silicone oils are described in US Pat. S. 4,798,679, 4,075,118 and EP 150,872.

Additional examples of all suds suppressors above are incorporated herein by reference, 199
P & G Case No. filed on November 6, 8 7332P, and 60/1
See, in the provisional patent application of Pramod K. Reddy entitled "Hydrophilicity Index for Aqueous Liquid Laundry Detergent Compositions Containing LAS", filed pursuant to the Patent Cooperation Treaty, having a patent number of 07,477.

The preferred particulate foam control agent used herein contains a silicone antifoam compound, an organic substance and a carrier substance, and the silicone antifoam compound and the organic substance are carried on the carrier substance. The carrier material is preferably natural starch or zeolite. Silicone antifoam compounds are polydiorganosiloxanes,
It is selected from the group consisting of solid silica and mixtures thereof. Preferably, the organic material is: (a) at least one fatty acid having a carbon chain of 12 to 20 carbon atoms (the organic material has a melting point of 45 to 80 ° C. and is insoluble in water); (B) at least one fatty alcohol having a carbon chain of 12 to 20 carbon atoms (the organic substance has a melting point of 45 to 80 ° C and is insoluble in water); (c) 12 carbon atoms A mixture of at least one fatty acid and at least one fatty alcohol having a carbon chain of ˜20 (the organic substance has a melting point of 45-80 ° C. and is insoluble in water); (d) Selected from organic substances consisting of fatty acid and glycerol monoesters having a carbon chain of 12 to 20 carbon atoms and a melting point of 50 to 85 ° C .; and (e) dispersible polymers; and mixtures thereof. Preferably, the dispersible polymer is selected from the group consisting of copolymers of acrylic acid and maleic acid, polyacrylates and mixtures thereof.

[0125]   Usable silicone suds suppressors known in the art are, for example, 1981 5
US Patents 4,265,779 and 199 to Gandolfo et al., Issued May 5,
European patent application 89307851.9 of Starch, M.S., published Feb. 7, 2000
It is disclosed in. Silicone defoamers and foam control agents in granular detergent compositions
To Bartolotta et al., US Patent 3,933,672 and March 24, 1987.
No. 4,652,392 issued to Baginski et al. here
Exemplary silicone-based suds suppressors useful in are:   (A) Polydimethylsiloxae having a viscosity of about 20 to about 1500 cs at 25 ° C.
Fluid   (B) About 0.6: 1 to about 1.2: 1 (CH_Three)_ThreeSiO_1/2Unit vs. SiO _Two SiO in unit ratio_TwoUnit (CH_Three)_ThreeSiO_1/2A system composed of units
Roxane resin, about 5 to about 50 parts by weight / (i) 100 parts, and   (C) Solid silica gel about 1 to about 20 parts by weight / (i) 100 parts Is a foam control amount of a granular foam control agent.   An additional suds suppressor suitable for use in the present invention was issued on June 9, 1998.
Are further described in US Pat. No. 5,762,647 to Brown et al.

(E) Transfer Inhibitors and Other Fabric Care Ingredients- The compositions of the present invention also contain one or more substances effective to prevent migration of dye from one fabric to another during the cleaning process. You may These agents may be contained in either the non-aqueous surfactant-containing liquid phase or the solid particulate material. Usually, such dye transfer inhibitors include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanines, peroxidases and mixtures thereof. These agents are typically about 0.01 to about 10% by weight of the composition, preferably about 0.01 to about 5%, more preferably about 0.05 to about 2%.

[0127] More specifically, where using the preferred polyamine N- oxide polymers The following structural formula: R-A x _-P contain units having the; wherein P is a polymerisable unit , To which an NO group may be attached, or the NO group may form part of a polymerizable unit, or the NO group may be attached to both units; A is of the structure: NC
One of (O)-, -C (O) O-, -S-, -O-, -N =; x is 0
Or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or cycloaliphatic group or a combination thereof, to which the nitrogen of the NO group may be attached, or N The -O group is part of these groups. Preferred polyamine N-oxides are when R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and their derivatives.

[0128]   The NO group can be represented by the following general structure:

[Chemical 20] In the above formula, R ₁ , R ₂ and R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or a combination thereof, x, y and z are 0 or 1, and an N—O group The nitrogen of may be attached or may form part of any of the above groups. Polyamine N-
The amine oxide units of the oxide have a pKa <10, preferably pKa <7, more preferably pKa <6.

Any polymer backbone may be used as long as the amine oxide polymer formed is water soluble and dye transfer inhibiting. Examples of suitable polymer backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include
There are random or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is an N-oxide. Amine N-oxide polymers are typically 10: 1 to 1: 1,000,000 amines to amine N-oxides.
It has a ratio of oxides. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by suitable copolymerization or with a suitable degree of N-oxidation. Polyamine oxides can be obtained with almost any degree of polymerization. Typically, the average molecular weight is 500 to 1,000,000, more preferably 1000 to 5
It is in the range of 0,000, most preferably 5000 to 100,000. The most preferred polyamine N-oxide useful in the present detergent composition is about 50,000.
A poly (having an average molecular weight of 0 and an amine to amine N-oxide ratio of about 1: 4.
4-vinylpyridine-N-oxide). This preferred type of material is "PV
It is called "NO".

Another suitable dye transfer inhibitor is Panandiker, published November 14, 1995.
See US Pat. No. 5,466,802, incorporated herein by reference. In addition to the dye transfer inhibitor, the present invention further comprises additional agents that exert a fabric care effect. As mentioned above, these additional agents may be necessary because the high concentration of the detergent composition in the aqueous laundry solution used in the present invention impairs contact of the aqueous laundry solution with clothing and fabric.

Therefore, in the present invention, a substance that is associated with the fabric and textile fibers that have been laundered with the product to reduce or minimize the tendency of the laundry fabric / textile to have a poor appearance is also added to the laundry product. You may Such detergent product additives can, of course, affect the appearance and integrity of the fabric without unduly hindering the laundry product's ability to perform its intended function. Such fabric appearance effects include, for example, improved overall appearance of the laundry fabric, suppression of pill and fluff formation, protection from fading, and improved abrasion resistance.

One such fabric care agent that acts specifically to prevent dye migration from the surface of clothing into the aqueous wash solution, yet exerts other fabric care effects, includes 30 polyethyleneimines having the general formula: It is PEI600E20:

[Chemical 21] In the above formula, B is a continuous portion due to branching of the polyethyleneimine main chain. E is the ethyleneoxy units having the _{formula: - (CH 2 CH 2 O} ) m H above wherein m has an average value of about 20. What is meant herein by an average value of 20 is that sufficient ethylene oxide or other suitable reactant has been reacted with the polyethyleneimine starting material to fully ethoxylate each NH unit to a degree of 20 ethoxylation. Is Rukoto. However, one skilled in the art will appreciate that some NH units hydrogen atoms will be substituted with less than 20 ethoxy units and some substituted with more than 20 ethoxy units, resulting in an average ethoxylation number of 20. You will understand.

The units constituting the polyalkyleneimine main chain are primary amine units having the formula: H ₂ N—CH ₂ CH ₂ ]-and —NH ₂ (forming the ends of the main chain and the branched chain). ), A secondary amine unit having the formula:

[Chemical formula 22] (After modification, those hydrogen atoms are replaced on average by 20 ethyleneoxy units) and a tertiary amine unit having the formula:

[Chemical formula 23] (The branch point of the book and the secondary main chain, and B represents the continuous portion of the chain structure due to branching). The tertiary unit has no replaceable hydrogen atoms and is therefore not modified by substitution with ethyleneoxy units. Cyclization can also occur during the formation of the polyamine backbone, so that some amount of cyclic polyamine can be present in the parent polyalkyleneimine backbone mixture. Each primary and secondary amine unit of the cyclic alkyleneimine is modified by the addition of alkyleneoxy units, similar to linear and branched polyalkyleneimines.

The indices w, x and y have values such that the average molecular weight of the polyethyleneimine backbone before modification is about 600 Daltons. In addition, one of ordinary skill in the art will appreciate that each branch must end with a primary amine unit, so that in the absence of a cyclic amine backbone, the value of index w will be y + 1. Each ethylene backbone unit -NCH ₂ CH ₂ - average molecular weight of about 43 daltons.

The polyamine of the present invention can be produced, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid and the like. A specific method for making these polyamine backbones is described in Ulrich et al. US Pat. No. 2,182,30 issued Dec. 5, 1939.
6; Mayle et al., US Pat. No. 3,033,746, issued May 8, 1962.
Esselmann et al., US Patent 2,208,0, issued July 16, 1940.
95; Crowther US Patent 2,806,8, issued September 17, 1957.
39; and Wilson US Patent 2,553, issued May 21, 1951.
, 696, all incorporated herein by reference.

Other fabric care agents suitable for use in the present detergent composition include dye-retaining polymers.
One example of such a polymer is an imidazole-epichlorohydrin adduct:

[Chemical formula 24] It has an imidazole: epichlorohydrin ratio of 1.36: 1. Additional dye-retaining polymers and dye-retaining parameter tests are included in P & G Case No. 5, incorporated herein by reference. 60 / 126,074 "Laundry Detergent Composition with Positively Charged Dye Retaining Polymer", filed March 25, 1999, having 7488P, and is described in a co-pending provisional application to Rajan K. Panandiker et al. As mentioned above, these dye-maintaining polymers exert an overall fabric care benefit in addition to color care protection.

(F) Thickening, viscosity-modifying and / or dispersant- The detergent composition optionally also comprises polymeric substances which act to enhance the ability of the composition to maintain its solid particulate ingredients in suspension. To do. Such substances act as thickeners, viscosity modifiers and / or dispersants. Such materials are mostly polymeric polycarboxylates,
Other polymeric materials such as polyvinylpyrrolidone (PVP) or polyamide resins may also be used.

Polymeric polycarboxylate materials may be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. There is. The presence of monomer segments having no carboxylate groups, such as vinyl methyl ether, styrene, ethylene, etc., in the polymer polycarboxylates is suitable provided that such segments do not account for more than about 40% by weight of the polymer. Is.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers useful herein are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form is preferably about 2000-1.
It is preferably about 200,000, more preferably about 2000 to 10,000, even more preferably about 4000 to 7000, most preferably about 4000 to 5000. Water-soluble salts of such acrylic acid polymers include, for example, alkali metal salts. Soluble polymers of this type are known substances. The use of this type of polyacrylate in detergent compositions is described, for example, in Diehl US Pat.
It is disclosed in Japanese Patent No. 3,308,067. Such substances can also exert a builder function. Other suitable polymeric materials suitable for use as thickening, viscosity modifying and / or dispersing agents include castor oil derivatives, polyurethane derivatives and polyethylene glycol polymers.

If utilized, any thickening, viscosity modifying and / or dispersing agent may be present at about 0.1
It should be present in the composition to the extent of ~ 4% by weight. More preferably, such material is about 0.1-2% by weight of the detergent composition.

(G) Soil Removal / Redeposition Agents- The compositions of the present invention may optionally also contain a water soluble ethoxylated amine having soil removal and antiredeposition properties. If used, the soil material can comprise from about 0.01 to about 5% by weight of the composition.

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Illustrative ethoxylated amines are further described in VanderMeer US Pat. No. 4,597,898 issued Jul. 1, 1986. Another one
One group of preferred soil remediation and anti-redeposition agents are the cationic compounds disclosed in Oh and Gosselink European patent application 111,965 published June 27, 1984. Other usable soil stain removal / redeposition inhibitors include 198
Ethoxylated amine polymers disclosed in Gosselink's European Patent Application 111,984, published June 27, 4; Gossel, published July 4, 1984.
Bipolar Polymers Disclosed in Ink European Patent Application 112,592; 1985 1
There is an amine oxide disclosed in Connor US Pat. No. 4,548,744 issued on Oct. 22. Preferred ethoxylated quaternary amine materials are selected from the group consisting of compounds having the general formula:

[Chemical 25] In the above formula, each x is independently less than about 16, preferably about 6 to about 13, more preferably about 6 to about 8, or each x is independently greater than about 35. Materials suitable for use in the present invention as described above include BASF Corporation and Witco Chemic of Germany.
Available from al Company.

It has been found that the degree of ethoxylation is important for the viscosity of the final detergent composition described herein. Especially for the following general structures:

[Chemical formula 26] When x is less than about 13, the ethoxylated quaternary amine clay material can be added to the liquid heavy duty detergent composition as a liquid at low temperatures without causing undesirable thickening. Similarly, with the same structure and a degree of ethoxylation greater than about 35, i.e., x greater than about 35, these highly ethoxylated materials will not melt at elevated temperatures without causing low temperature product thickening, It can be added to the formulation as a stable solid.

Of course, other conventional optional brightener type compounds are also optionally used in the composition to exert the conventional fabric "whitening" effect rather than the true dye transfer inhibiting effect. That would be obvious. Such uses are customary and well known in detergent formulations. Other soil decontamination and / or anti-redeposition agents known in the art may also be utilized in the composition. Another type of preferred anti-redeposition agent is the carboxymethyl cellulose (CMC) material. These materials are well known in the art.

(H) Liquid Bleach Activator- The detergent composition may optionally also contain a bleach activator, which is liquid at room temperature and is added to the liquid phase of the detergent composition as a liquid. You can One such liquid bleach activator is glycerol triacetate, which acts as a solvent in the composition during storage, but is peroxidized when released into the wash solution and functions as a bleach activator. To do. Other examples of bleach activators are acetyl triethyl citrate (ATC) and nonanoyl valerolactam. The liquid bleach activator can be dissolved in the liquid phase of the composition.

(I) Whitening agents, dyes and / or perfumes -The detergent compositions also optionally contain conventional whitening agents, bleach catalysts, dyes and / or perfume substances. Such brighteners, silicone oils, bleach catalysts, dyes and fragrances, of course, must be compatible and non-reactive with other composition components in an aqueous or non-aqueous liquid environment.
If present, brighteners, dyes and / or fragrances are typically about 0.0001 to 2% by weight of the composition.

(J) Structural Elastomer- The liquid detergent composition comprises from about 0.1 to 5% by weight, preferably about 0.1.
1-2% of fine solid particulate material may also be included, including silica such as fumed silica, titanium dioxide, insoluble carbonate, fine carbon, SD-3 or combinations of these materials. Clay is also well known to those skilled in the art and is commercially available from companies such as Rheox. This type of finely divided material functions as a structural elasticizer in the products of the invention. Such materials have an average particle size of about 7-40 nm, more preferably about 7-15 nm. Such materials also have a specific surface area of about 40-400 m ² / g. The microelastomer material may improve the transport stability of the present liquid detergent product by increasing the elasticity of the surfactant build liquid phase without increasing the product viscosity. This allows such products to withstand the high frequency of vibrations found during shipping without undergoing undesirable structural collapse that can cause precipitation in the product. In the case of titanium dioxide, the use of this material also imparts whiteness to the suspension of particulate material within the detergent composition. This effect improves the overall appearance of the product.

(K) Microspheres-Microspheres may also be used in the present invention. Suitable microspheres may be made from one or more water insoluble materials selected from the group consisting of polymers, siliceous materials, ceramics and mixtures thereof. For a more detailed description of microspheres, see “Microencap
sulation ”, Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition
, Volume 16, pages 628-651 (John Wiley & Sons, Inc., 1979); hereby incorporated by reference. The polymer microspheres of the present invention are preferably thermoplastics, acrylonitrile,
It is made from a water-insoluble material selected from the group consisting of methacrylonitrile, polyacrylonitrile, polymethacrylonitrile and mixtures thereof. The siliceous microspheres of the present invention are preferably made from one or more siliceous materials selected from the group consisting of glass. Borosilicate glass is particularly preferred. Commercially available microspheres are trade name EXPANCEL ^R , Swedish Akzo-Nobel; trade name PM6
545, PM6550, PM7220, PM7228, EXTENDOSPHERES ^R , LUXS
IL ^R , Q-CEL ^R , SPHERICAL ^R PQ Corp .; trade name ALBUMEX ^R from Malinckrodt.

For a more detailed disclosure of suitable examples of microspheres and liquid detergent containing microspheres, see P & G Case No. 5, incorporated herein by reference. 7417P, provisional application 60/11
See co-pending provisional patent application to Broeckx et al., Entitled "Stable Non-Aqueous Liquid Laundry Detergent Containing Low Density Particles," filed February 10, 1999, having 9,555. In addition to the types of microspheres described above, microspheres suitable for use in the present invention may be made from washed water-soluble biological materials such as starch and proteins, which are P & G.
Case No. Further details are disclosed in the co-pending provisional patent application of Sadlowski et al., Entitled "Non-Aqueous Liquid Detergent with Cleaning Water-Soluble Low Density Filler Particles," filed August 10, 1999, having 7707P, which is incorporated herein by reference. Incorporated here for.

In addition, the microspheres used in the present invention may be used as a core for particles formed by substantially encapsulating the core with a detergent component. A non-limiting list of such ingredients includes organic and inorganic builder materials, alkali source materials and other coating ingredients. These coated microspheres are incorporated herein by reference, P
& G Case No. Filed on August 10, 1999, having 7708P
Further details are disclosed in the co-pending provisional patent application of Aouad et al. Entitled "Washing Water-Soluble Low Density Filler Particle-Containing Non-Aqueous Liquid Detergent." Coated microspheres are incorporated previously.
& G Case No. It is also described in the copending provisional application of Sadlowski et al., 7707P.

(I) Effervescent agent-In another preferred embodiment of the present invention, the tablet further comprises an effervescent agent. Foaming as described herein means the generation of gas bubbles from a liquid as a result of a chemical reaction between a soluble acid source and an alkali metal carbonate, which gives rise to carbon dioxide gas: C ₆ H ₈ O ₇ +3 NaHCO ₃ → Na ₃ C ₆ H ₅ O ₇ + 3CO ₂ +3
Another example of H ₂ O acid and carbonate sources and other foaming systems is (Pharmaceutical Dosage Forms: Tabl
ets Volume 1, Page 287-291).

Effervescent agents may also be added to the tablet mix in addition to the detergent ingredients. The addition of this effervescent agent to detergent tablets improves tablet disintegration time. The amount is preferably 5 to 20% by weight of the tablet, most preferably 10 to 20%. Preferably, the blowing agent should be added as an agglomerate of different particles or as compact particles which are not separated. Due to the gas generated by effervescence in the tablet, the tablet can have a higher DFS while still having a disintegration time similar to non-effervescent tablets. Effervescent tablet DF
Disintegration of effervescent tablets is faster when S is maintained as is the case with tablets that are not. Further dispersion aids may be provided by using compounds such as sodium acetate or urea. A list of suitable dispersion aids is Pharmaceutical Dosage Forms: Tab
lets, Volume 1, Second edition, Edited by HALieberman et al, ISBN 0-8247-8
Also seen in 044-2. The foaming system may contain acids and bases, such as citric acid and sodium bicarbonate, and / or the foaming system contains enzymes such as catalase and / or peroxidase, and a peroxide source such as hydrogen peroxide. You may.

(M) Binder -non-gelling binder may also be incorporated into the tablet-forming particles to further facilitate dispersion. When a non-gelling binder is used, suitable non-gelling binders include synthetic organic polymers such as polyethylene glycol, polyvinylpyrrolidone, polyacrylates and water soluble acrylate copolymers. Handbook of Pharmaceutical E
The xcipients, second edition has the following binder classifications: gum arabic, alginic acid, carbomer, sodium carboxymethyl cellulose, dextrin, ethyl cellulose, gelatin, guar gum, hydrogenated vegetable oil type I, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, liquid. glucose,
Aluminum magnesium silicate, maltodextrin, methyl cellulose, polymethacrylate, povidone, sodium alginate, starch and zein.
Most preferred binders, such as cationic polymers, i.e. ethoxylated hexamethylenediamine quaternary compounds, bishexamethylenetriamine or others, such as pentaamines, ethoxylated polyethyleneamines, maleic acid acrylic polymers, also have an active cleaning function in laundry washing. Have

Since the non-gelling binder material is preferably sprayed, a suitable temperature of 90 ° C. or lower, preferably 70 ° C. or lower, even more preferably 50 ° C. or lower so as not to damage or decompose other active ingredients in the matrix. It has a high melting point. Most preferred is
A non-aqueous liquid binder (ie not an aqueous solution) that is sprayed in the molten state.
However, they should be binding within the tablet, although they may be solid binders which are incorporated into the matrix by dry addition. The non-gelling binder material is preferably in the range of 0.1 to 15% by weight of the composition, more preferably 5% or less, especially 2% or less of the tablet if it is a non-laundry active. Used in.

Gelling binders such as nonionic surfactants preferably avoid their liquid or molten form. Nonionic surfactants and other gelling binders are not excluded from the composition, but they are preferably incorporated into detergent tablets as a component of the particulate material rather than as a liquid.

(N) Clay-The clay mineral used to exert the softening properties of the composition is an expansive three-layer clay with an ion exchange capacity of at least 50 meq / 100 g clay, namely aluminosilicate and magnesium silicate. Can be expressed as The term "expandable" used to describe a clay relates to the ability of a laminated clay structure to swell or expand upon contact with water. Used here 3
Layer-expanding clay is a material that is classified geologically as smectite.

There are two different types of smectite type clays; in the first type aluminum oxide is present in the silicate crystal lattice; in the second type of smectite magnesium oxide is present in the silicate crystal lattice. The general formula of these smectites is aluminum oxide and magnesium type clay, and Al ₂ (S
i ₂ O ₅ ) ₂ (OH) ₂ and Mg ₃ (Si ₂ O ₅ ) ₂ (OH) ₂ . It will be appreciated that the hydrate water range in the above formula will vary depending on the processing to which the clay has been applied. This is not critical to the use of the smectite clay in the present invention, as the expansive character of the hydrated clay depends on the silicate lattice structure. Furthermore, although atomic substitution with iron and magnesium can occur within the crystal lattice of smectite, not only H ⁺ but also metal cations such as Na ⁺ and Ca ⁺⁺ give rise to electrical neutrality, so that water of the hydrate is added. May coexist. However, as will be described later, such cation substitution is not critical to the use of the clay herein, as it does not substantially change the desired physical properties of the clay.

The trilayer expandable aluminosilicates useful herein are further characterized by a 28-sided crystal lattice, and the expandable 3-layer magnesium silicate has a 38-sided crystal lattice. As mentioned above, the clay used in the composition of the present invention contains cationic counterions such as protons, sodium ions, potassium ions, calcium ions, magnesium ions and the like. It is customary to distinguish between clays on the basis of one cation absorbed mainly or exclusively. For example, sodium clay is one in which the cations absorbed are predominantly sodium. The thus absorbed cation becomes involved in the exchange reaction with the cation existing in the aqueous solution.
A typical exchange reaction for smectite-type clay is represented by the following formula: smectite clay (Na) + NH ₄ OH → smectite clay (NH ₄ ) + NaOH

In the above equilibrium reaction, one equivalent of ammonium ion is replaced by one equivalent of sodium, so that the cation exchange capacity (sometimes referred to as “base exchange capacity”) is measured in milliequivalent / 100 g of clay (meq / 100 g). It is customary to measure. The cation exchange capacity of clays can be measured by several techniques, including electrodialysis, titration after exchange with ammonium ions, or methylene blue procedure, all of which are Grimsh.
aw, "The Chemistry and Physics of Clays", pp.264-265, Interscience (1971). The cation exchange capacity of clay minerals is associated with factors such as clay swellability, clay charge (which is at least partially investigated by the lattice structure). The ion exchange capacity of clay is about 2 meq / 100g of kaolinite.
To about 150 meq / 100 g or more of clay with montmorillonite seeds. Illite clay has an ion exchange capacity of about 26 meq / 100 g in the lower part of the range, in the case of average illite clay.

Illite and kaolinite clays, which have a relatively low ion exchange capacity, are preferably not used as clays in the composition. In fact, such illite and kaolinite clays are the major constituents of clay and are removed from the fabric surface by the present composition as described above. However, nontonites, which have an ion exchange capacity of about 70 meq / 100 g, and smectites, such as montmorillonite, which have an ion exchange capacity of greater than 70 meq / 100 g, adhere to the fabric and provide the desired softening effect, It has been found useful in this composition. Thus, the clay minerals useful herein are characterized as expandable tri-layer smectite type clays having an ion exchange capacity of at least about 50 meq / 100 g.

Without wishing to be bound by theory, the advantageous softening (and possibly de-dyeing, etc.) effect of the composition is due to the physical characteristics and ion exchange properties of the clay used here. It seems to be obtained due to. That is, non-expandable clays such as kaolinite and illite, both clay species having an ion exchange capacity of less than 50 meq / 100 g, do not exhibit the beneficial aspects of the clay used in the composition. , Showed in the experiment.

All smectite clays used in the composition are commercially available. Such clays include, for example, montmorillonite, volkonskoite, nontronite,
There are hectorites, saponites, sauconites and vermiculites. These clays have various trade names, such as Geogia Kaolin Co., Elizabeth, New Jers.
ey to Thixogel # 1 and Gelwhite GP; American Colloid Co., Skokie, Illinois
To Volclay BC and Volclay # 325; International Minerals and Chemicals to Black Hills Bentonite BH450; RT Vanderbilt to Veegum Pro and Veegum F
It is commercially available at. It will be appreciated that such smectite type minerals obtained under the trade name may be a mixture of various individual minerals. Such mixtures of smectite minerals are suitable for use herein.

While any smectite type clay having a cation exchange capacity of at least about 50 meq / 100 g is useful herein, some clays are preferred. For example, Gelwhi
te GP is a very white form of smectite clay and is therefore preferred when formulating white granular detergent compositions. Volclay BC, a smectite-type clay mineral that contains at least 3% iron (expressed as Fe ₂ O ₃ ) in its crystal lattice and has a very high ion exchange capacity, is the most efficient for use in laundry compositions. It is one of the effective clays and is preferable from the viewpoint of product performance.

Clay minerals suitable for use herein may be selected from the fact that smectite exhibits a true 14Å x-ray diffraction pattern. This characteristic pattern, when combined with the exchangeability measurements made as described above, provides a basis for selecting the specific smectite-type minerals used in the granular detergent compositions disclosed herein. The clay is preferably predominantly in the form of granules, at least 50% (preferably at least 75% or at least 90%) of at least 100 μm and within 1800 μm,
It preferably takes the form of granules having a size within 1180 μm, preferably 150-850 μm. Preferably, the amount of clay in the granules is at least 5 of the granules.
0% by weight, usually at least 70% or 90%.

(O) Flocculants- Most clay flocculating polymers are fairly long chain polymers derived from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinylpyrrolidone and ethyleneimine. And copolymers. Gums such as guar gum are also suitable. Polymers of ethylene oxide, acrylamide or acrylic acid are preferred.
These polymers dramatically increase the adhesion of fabric softening clays if their molecular weight is in the range 100,000 to 10 million. Such polymers having a weight average molecular weight of 150,000 to 5 million are preferred. The most preferred polymer is poly (ethylene oxide). The molecular weight distribution can be easily examined using gel permeation chromatography against a narrow molecular weight distribution poly (ethylene oxide) standard.

The amount of flocculant is preferably 0.5-10% by weight of the tablet, most preferably about 2%.
6%. The flocculant preferably takes the form of predominantly granules, at least 50% by weight (preferably at least 75%, most preferably at least 90%) of at least 100 μm 18
Within 00 μm, preferably within 1180 μm, most preferably 150 to 850 μm
Take the form of granules with a size of m. Preferably, the amount of flocculant in the granule is at least 50% by weight of the granule, usually at least 70% or 90%.

Other ingredients commonly used in detergent compositions and which may be incorporated into the detergent tablets of the present invention include chelating agents, soil release agents, soil redeposition inhibitors, dispersants, brighteners, foams. There are inhibitors, fabric softeners, dye transfer inhibitors and fragrances. It should be noted that improved disintegration or dispensability is obtained when the clay material is compressed prior to incorporation into tablets or cleaning compositions. For example, tablets containing clay compressed prior to compounding into tablets will disintegrate faster than tablets containing similar clay materials that were not compressed prior to compounding into tablets. In particular, the amount of pressure used to compress the clay is important in obtaining the clay particles that aid in disintegration or distribution. Moreover, when the softening clay is compressed and then incorporated into the cleaning composition or tablet, not only improved disintegration or dispersibility but also good softness of the fabric is obtained. Preferably, the clay component is obtained by compression of clay material.

A preferred process consists of subjecting the clay material to a pressure of at least 10 MPa or even at least 20 MPa or even 40 MPa. This may be done, for example, by compressing or roller compacting the clay material, optionally with one or more other ingredients, to form clay tablets or sheets, preferably followed by size such as compression clay sheets or crushing of the tablets. This can be done by forming compressed clay particles by reduction. The particles are then incorporated into tablets or cleaning compositions. Tableting and roller compaction methods are known in the art. For example, clay compacts are sold by the Fitzpatrick Company, Lloyd 50K tablet press or Chilso.
It can be done with a nator roller compactor.

For a better understanding of the present invention, reference is made to the following examples, which are for purposes of illustration only and not for limiting the scope. The following examples are given for illustrative purposes only and should not be construed as limiting the scope of the appended claims in any way.

In the abbreviation detergent compositions used in the examples , the abbreviated component designations have the following meanings: LAS: sodium linear C _11-13 alkylbenzene sulfonate TAS: sodium tallow alkyl sulphate C45AS: sodium _C 14 _{-C 15} alkyl sulfates C45E3S: 3 moles of ethylene oxide condensed with sodium _C 14 _{-C 15} alkyl sulfates ^{_{QAS: R 2 N + (CH}} 3) 2 (C 2 H 4 OH) (R 2 = C 12 -C ₁₄ ) Soap: a sodium linear alkylcarboxylate zeolite A obtained from an 80/20 mixture of tallow and coconut oil A: Formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ having a main particle size in the range of 0.1-10 μm 27H ₂ O hydrated sodium aluminosirike (Weight expressed on an anhydrous basis) NaSKS-6: crystalline layered silicate of the formula δ-Na ₂ Si ₂ O ₅ citric acid: anhydrous citric acid carbonate: anhydrous sodium carbonate bicarbonate with a particle size of 200-900 μm Salt: Anhydrous sodium bicarbonate silicate having a particle size distribution of 400 to 1200 μm: Amorphous sodium silicate (SiO ₂ : Na ₂ O = 2.0: 1) Sulfate: Anhydrous sodium sulfate Mg sulfate: Anhydrous magnesium sulfate citrate : Trisodium citrate dihydrate MA / AA with a particle size distribution of 425-850 μm MA / AA 1: 4 maleic / acrylic acid copolymer, average molecular weight about 70,000 AA: sodium with average molecular weight 4500 Polyacrylate polymer CMC: Sodium carboxymethyl cellulose protease: O95 / 10591, sold by Genencor Int. Inc., a proteolytic enzyme cellulase with 4% by weight of active enzyme: sold by NOVO Industries A / S under the trade name Carezyme 0.23. Amylase, a cellulolytic enzyme with wt% active enzyme: 1.6% by weight starch degrading enzyme lipase with active enzyme sold under the tradename Termamyl 120T by NOVO Industries A / S: NOVO Industries under the brand name Lipolase A lipolytic enzyme perborate having 2.0% by weight of active enzyme sold by A / S: sodium perborate percarbonate: sodium percarbonate NOBS: sodium salt form of nonanoyloxybenzenesulfonate NAC-OBS :( 6-nonamidocaproyl) oxybenzene sulfonate TAED: tetraacetylethylenediamine DTPA : Diethylenetriaminepentaacetic acid EDDS: sodium salt form of ethylenediamine-N, N'-disuccinic acid, (S, S) isomer photoactivated bleach: sulfonated zinc phthalocyanine CHDM encapsulated in dextrin soluble polymer CHDM: 1,4 -Cyclohexanedimethanol whitening agent: 4,4'-bis [(4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino] stilbene-2,2'-disulfonic acid disodium HEDP : 1,1 hydroxyethane diphosphonic acid PEGx: polyethylene glycol having a molecular weight of x (typically 4000) 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 (n = 20 30)
SRP: diethoxylated poly (1,2-propylene terephthalate) short block polymer silicone antifoam: having a foam modifier: dispersant ratio of 10: 1 to 100: 1, containing siloxane-oxyalkylene copolymer as dispersant Polydimethylsiloxane suds modifier In the following examples, all levels are given as weight percent of the composition:

Liquid Product Formulation Examples Example I A non-aqueous liquid detergent composition consisting of a surfactant-rich liquid phase and a solid phase was prepared as follows: wt% Composition A Composition B Nonionic Surfactant 21. 27 20.14 BPP solvent 18.30 17.33 LAS surfactant 15.83 14.99 Ethoxylated quaternary amine clay material 1.29 1.22 Hydrotrope 4.80 0.00 Na citrate dihydrate 6. 73 6.37 Na carbonate 9.89 9.37 Bleach activator 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 enzyme 0.79 0.75 Antifoaming agent 0.61 0.85 Plastic microspheres 0.51 0.49 Titanium dioxide 0.50 0.4 Brighteners 0.20 0.19 PEG8000 0.40 0.38 perfume 1.72 1.63 Other 2.16 2.15

Liquid detergent composition A was prepared according to the present invention, which contains the preferred hydrotrope 1,4-cyclohexanedimethanol. As noted above, Liquid Detergent Composition B was nearly identical to Composition A, except that Composition B did not contain any hydrotrope, so the other ingredients were readjusted somewhat. The effects of the hydrotropes described herein are readily investigated in experiments measuring the elution rate of liquid detergent compositions in water. Rate of liquid detergent product elution in underwater testing Place 3 L of deionized water in a glass beaker at about 25 ° C. Place a 2.5 cm magnetic stir bar and conductive electrode in water. Water is mixed in at a speed of 400 rpm and this constant speed is maintained throughout the experiment. 3. Place an 85 ml capacity screen cup with a 60 mesh screen in the center of the beaker from the surface of the water so that the top of the cup is located just above the water and the water does not enter from the top, but only through the screen. 4. Very slowly add 1 ml of liquid detergent product to the center of the screen cup (from a syringe). This is To. The conductivity of To is measured. 5. The measurement of the electrical conductivity of the detergent product-water mixture is repeated at regular intervals, for example after 0.5, 1, 2, 4, 6 and 10 minutes. 6. After a suitable amount of time (eg, 10 minutes), soak the cup in the mixture,
The liquid detergent product that remains inside the screen cup is added to the product-water mixture by increasing the stirring speed. 7. When all products have eluted and the conductivity has reached a steady state value, record the value.

Both of these compositions were tested using the "rate of liquid detergent product elution in the underwater test" thus detailed. The conductivity was measured by immersing the electrode in water at the beginning of the test detergent composition solution to determine percent elution and conductivity. I got the following results: Composition A Composition B Time Conductivity Elution% Conductivity Elution% 0s (To) 0 0 0 0 30s 28 19 19 12 7 60s 40 27 17 17 10 120s 54 37 37 23 14 180s 62 42 31 31 18 240s 68 47 39 23 23 360s 53 44 26 600s 81 55 49 49 29 660s 91 62 51 30

After 11 minutes, the total dissolution of the detergent composition was forced by high agitation to measure the conductivity: Total dissolution 100 100 146 100 Elution value was measured conductivity at each individual time measured conductivity at total dissolution Obtained by dividing by and multiplying by 100.

[0175] EXAMPLE II An aqueous liquid detergent composition according to the present invention is prepared as follows: Composition C Ingredient Wt% C _12-15 alkyl ether (2.5) sulfate 18.0 C _12-13 alkyl ethoxylate (9.0) 2.00 C _12-14 glucose amide 3.50 Citric acid 3.00 C _12-14 fatty acid 2.00 CHDM 5.00 MEA up to pH 8 ethanol 3.0 propanediol 6.0 dyes, fragrances, Whitening agent, enzyme, preservative, foam control agent, other, water balance 100%

Example III A non-aqueous liquid detergent composition consisting of a liquid phase and a solid phase rich in surfactant was prepared as follows: wt% composition composition composition composition composition A B C D E NaLAS 14.6. 14.9 13.9 13.0 14.9 HLAS 0.0 0.0 1.0 1.9 0.0 Nonionic surfactant 20.6 20.7 20.7 20.7 20.7 Na citrate dihydrate 3.3 3.3 3.3 3.3 3.3 Copolymer of acrylic acid and maleic acid 2.9 2.9 2.9 2.9 2.9 EDDS 1.2 1.2 1.2 1.2 1.2 Ethoxyl Chemical quaternary amine clay material 1.3 1.3 1.2 1.3 1.3 Sodium perborate 11.5 11.5 11.5 11.5 11.5 Bleach activator 2.9 5.8 2.9 2.9 2.9 Triacetin 12.5 0.0 12.5 12.5 8.7 Na 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 enzyme 0.8 0.8 0.8 0.8 0.8 Duramyl enzyme 0.8 0.4 0.4 0.4 0.4 Mannanase enzyme 0.2 0.2 0.2 0.2 0.2 Carezyme Element 0.1 0.0 0.0 0.0 0.0 Whitening agent 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 Perfume 1.7 1.7 1.7 1.7 1.7 Silicone 0.7 0.7 0.7 0.7 0.7 Silicone surfactant DC 3225 0.3 0.3 0.3 0.3 0.3 Hydrogen Chemical C _16-18 Sodium salt of fatty acid 0.5 0.5 0.5 0.5 0.5 Others Remainder Remainder Remainder Remainder

Granule / Powder Product Formulation Example Example I The following compositions are according to the invention. ABCDE FGH 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 ‐ ‐ ‐ ‐ MgSO ₄ 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 ‐ ‐ ‐ ‐ ‐ Whitening agent 0.05 0.05 0.05 ‐ 0.05 ‐ ‐ ‐ ‐ Silicone oil 0.01 0.01 0.01 ‐ ‐ 0.01 ‐ ‐ ‐ Aggregate LAS ‐ ‐ ‐ ‐ ‐ ‐ 0.2 0.2 0.01 C ₄₅ A S - - - - - - 2.0 - 1.0 AE ₃ - - - - - - - 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 ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ‐ ‐ ‐ ‐ ‐ ‐ ‐ aggregates SKS-6 6.0 ‐ ‐ ‐ 6.0 3.0 ‐ 7.0 10.0 LAS 4.0 5.0 ‐ ‐ 5.0 3.0 ‐ 10.0 12.0 Dry addition granular 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 ‐ LA (Flake) 10.0 10.0 - - - - - 8.0 - Spray-on 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 - Perfume - - - 0.8-0.5-0.5- Dry-added 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 --- Photobleach 0.02 0.02 0.02 0.1 0.05-0.3-0.03 Enzyme (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 Fragrance (encapsulated) 0.6 0.5 0.5 ‐ 0.3 0.5 0.2 0.1 0.6 Foaming inhibitor 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 Colored carbonate (blue, green) 0.5 0.5 1.0 2.0 ‐ 0.5 0.5 0.5 1.0 SKS-6 ‐ ‐ ‐ 4.0 ‐ ‐ 6.0 ‐ The composition up to 100% color has at least 90% by weight of particles having a geometric mean particle size of about 850 microns to about 1.2 geometric standard deviation of. Surprisingly, the composition has improved aesthetics, flowability and solubility.

[0178] Tablets product detergent base powder of Formulation Examples Example Ia i) composition A (see Table 1) were prepared as follows: by mixing together all the particulate material of base composition A in a mixing drum in , Formed a uniform granular mixture. ii) Base powder 9 of composition A while mixing 1 part of polyethylene glycol
Sprayed on 9 parts. iii) The tablets were then manufactured as follows. 54 g of the mixture were introduced into a 5.5 cm diameter circular mold and compressed with an Instron 4464 press at a force of 2.0 kN. The tablet tensile strength (or diametral breaking stress) obtained by this force was 19.2 kPa. Means for assessing tablet strength (also called diametral breaking stress) are described in Pharmaceutical d
osage forms: tablets, volume 1, Ed. HALieberman et al, published in 1989.

Example Ib i) The same Composition A was prepared following the same process as Example Ia. ii) 0.9 parts of polyethylene glycol and 0.1 part of 1,4-cyclohexanedimethanol were mixed together and sprayed onto 99 parts of the base powder of composition A with mixing. iii) The tablets were then manufactured following the same procedure as described in Example Ia. 2.
The tablet tensile strength (or diametral breaking stress) obtained with a force of 0 kN was 23.6 kPa. Examples 2a-3b were prepared in a manner similar to the process described above and according to the formulation composition detailed below. Table 1 Composition Composition Composition A (%) B (%) C (%) Anionic aggregate ¹ 34 34 34 Nonionic aggregate ² 9.57 9.57 9.57 Laminated silicate ³ 2.7 1.5 1.5 Sodium percarbonate 12.43 12.43 12.43 Bleach Acti Beta-aggregate ⁴ 6.48 6.48 6.48 Sodium carbonate 19.01 18.96 18.46 EDDS / sulfate particles ⁵ 0.50 0.50 0.50 Tetrasodium salt of hydroxyethanediphosphonic acid 0.8 0.8 0.8 Fluorescent agent 0.11 0.11 0.11 Zinc phthalocyanine sulfonate inclusion ⁶ 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 MW 4000 Polyethylene Glycol Flake-1.5 1.5 Linear Alkylbenzene Sulfonate / Diisopropylbenzene Sulfonate Sodium Salt ⁸ 1 1 1.5

1: Anionic aggregate consists of 37% anionic surfactant, 2% cationic surfactant, 22% layered silicate, 10% acetate, 6% carbonate and 23%.
% Zeolite. 2: The nonionic agglomerates consist of 24% nonionic surfactant, 6% ethoxylated hexamethylenediamine quat, 40% acetate / zeolite mix, 20% carbonate and 10% zeolite. 3: Laminated silicate consists of 95% SKS6 and 5% silicate. 4: Bleach activator agglomerates consisted of 81% TAED, 17% acrylic / maleic acid copolymer (acid form) and 2% water. 5: ethylenediamine N, N-disuccinic acid sodium salt / sulfate particles,
It consists of 58% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulphate and 19% water. 6: Zinc phthalocyanine sulfonate inclusions are 10% active. 7: The suds suppressor consists of 11.5% silicone oil (eg Dow Corning), 59% zeolite and 29.5% water. 8: The linear alkylbenzene sulfonate / diisopropylbenzene sulfonate sodium salt consists of 67% linear alkylbenzene sulfonate and 33% diisopropylbenzene sulfonate.

A tablet binder composition having the following composition was sprayed onto the above detergent base powders: 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% Then the tablet strength is determined according to the invention in step iii) and elsewhere above. Tested:

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 tablet samples containing CHDM is virtually the same except that it does not contain CHDM. The composition was larger than the CHDM tablet sample.

An operating window was also evaluated: Table 4 Example 3a Example 3b Density at tablet hardness of 5.5 kP 1035 1010 15% Density at tablet distribution 1052 1035 Tablet samples containing CHDM (width = 25 g / L) Operating window was wider than that of the tablet sample containing no CHDM (width = 17 g / L).

The dispensed doses of the detergent tablets shown in Table 4 can be determined from experiments measuring the amount of detergent product dispensed in an automated cleaning process as follows: Weigh two tablets nominally each 50 g, then placed into a dispenser of Baucknecht ^R WA9850 washing machine. Water supply to the washing machine is 20 ° C and 21 grains /
The hardness is set to gallon, and the flow rate of water introduced into the dispenser is set to 8 L / min. 2. The level of tablet residue remaining in the dispenser is checked by switching on washing on and setting the wash cycle to wash program 4 (white / color, short cycle). 3. The distribution residue rate is calculated as follows: Distribution rate = residue weight / plain tablet weight × 100 The residue level is examined by repeating the operation 10 times, and the average residue level is calculated based on 10 individual measurements. To do.

Although the present invention has been described in detail in this manner, various modifications can be made without departing from the scope of the invention, and the invention is not limited to the one described in the specification.
It will be apparent to those skilled in the art.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 3/42 C11D 3/42 17/06 17/06 17/08 17/08 (31) Priority claim number 60 / 156,339 (32) Priority date September 27, 1999 (September 27, 1999) (33) Country of priority claim United States (US) (31) Priority claim number 60 / 156,340 (32) Priority date September 27, 1999 (September 27, 1999) (33) Priority claiming country United States (US) (31) Priority claim number 60 / 188,123 (32) Priority date March 9, 2000 Day (March 3, 2000) (33) Country claiming priority US (US) (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, I, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZW) , EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, CA , CH, CN, CR, CU, CZ, DE, DK, DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, K E, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Jean-Pol, Boutique Bee-5030 Belgium, Jean-Blue, Liu, Emile, Laval, 32 (72) Inventor Walter, Auguste, Maria , Brex Belgian Belgium-9240, Zeer, Oud, Cooted Reef, 166 (72) Inventor Steven, Joseph, Lewis, Kuzeman Belgian Belgian Belgium-1910, Kampenhout, Ternstrast, 25 (72) invention Lorenzo, Mateo, Pierre, Garco Belgian Belgium-1853, Strombek-Bevel, Vieburstraat, 25 (72) Inventor James, Peot, Johnston Belgian Be-1785, Melteram, San, Gudurad Reef, 11 (72) ) Inventor Eric, Chuo Belgium-1000, Belgium, Brussels, Liu, De, Commersan, 45 (72 ) Inventor David, William, Angram Belgium B-1000, Brussels, Liu, Du, Lac, 54 F term (reference) 4H003 AB19 AC08 BA10 BA12 BA17 BA27 DA01 EA16 EA20 EA25 EA27 EB04 EB08 EB09 EB13 EB19 EB36 EB37 EC01 EC02 EC03 EE05 FA09 FA21 FA36 FA43

Claims (17)

[Claims] 1. A laundry detergent composition comprising a hydrotrope, the hydrotrope having a first polar group and a second polar group separated from each other by at least 5 aliphatic carbon atoms. A laundry detergent composition. 2. The composition is in liquid, non-aqueous liquid or aqueous liquid form, preferably at a concentration sufficient to allow the surfactant to form a viscous phase upon dilution with water in the absence of hydrotrope. An active agent-containing, more preferably characterized by a non-quaternary compound which is a derivative of any of C _16-18 unsaturated fatty acids, methyldiethanolamine and methyl chloride. Laundry detergent composition. 3. The laundry detergent composition according to claim 1 or 2, wherein the first polar group is a hydroxyl group —OH, and preferably both the first polar group and the second polar group are hydroxyl groups. . 4. The polar group is separated by 6 aliphatic carbon atoms, preferably the polar group is separated by 8 or less aliphatic carbon atoms, and more preferably the polar group is separated by 10 or less aliphatic carbon atoms. The laundry detergent composition according to any one of claims 1 to 3, which has been applied. 5. The hydrotrope is: (a) 1,4-cyclohexanedimethanol: (B) 1,6-hexanediol: (C) 1,7-Heptanediol: (D) The laundry detergent composition according to any one of claims 1 to 4, which is selected from the group consisting of a mixture thereof. 6. A detergent composition wherein the organic additive is a nonionic surfactant selected from the group consisting of glycerol triacetate, acetyltriethyl citrate or mixtures thereof, enzymes, ethoxylated quaternary amine substances and mixtures thereof. The laundry detergent composition according to any one of claims 1 to 5, further characterized by an ingredient selected from the group consisting of: 7. A composition comprising: A) 49 to 99.95% by weight of the composition of a non-aqueous surfactant-containing liquid phase; B) 1 to 50% by weight of the composition, substantially in the above liquid phase. Insoluble, peroxygen bleach, bleach activator, organic detergent builder, inorganic alkali source,
Granular material characterized by a material selected from the group consisting of enzymes, brighteners, polymers and mixtures thereof, C) characterized by a hydrotrope according to any one of claims 1 and 3-5. The laundry detergent composition according to any one of claims 1 to 6, which is a non-aqueous composition. 8. The detergent composition contains 0.01 to 10% of fabric care agent.
The non-aqueous liquid detergent composition according to claim 1. 9. The non-aqueous liquid detergent composition according to any one of claims 1 to 8, wherein the surfactant-containing non-aqueous liquid phase has a density of 0.6 to 1.4 g / cc. object. 10. The non-aqueous liquid detergent composition according to any one of claims 1-9, wherein the particulate material has a particle size of 0.1-1500 microns. 11. The non-aqueous liquid detergent composition according to claim 1, further characterized by microspheres having a median particle size of 10 to 150 μm. 12. The non-aqueous liquid detergent composition according to claim 1, further characterized by microspheres having an average density of 0.1-1.8 g / ml. 13. A method of laundering a soiled fabric, characterized by the step of contacting the fabric in an aqueous wash solution containing the non-aqueous liquid detergent composition according to any one of claims 1-12. 14. A method of laundering a soiled fabric characterized by the step of contacting the fabric in an aqueous laundry solution containing a laundry detergent composition according to any one of claims 1-13. 15. The composition is in granular form, preferably the granular laundry detergent composition comprises: i) a binder, a first polar group and a second group separated from each other by at least 5 aliphatic carbon atoms. 15. Hydrotrope 0.01-3% by weight ii) characterized by comprising organic molecules with polar groups ii) characterized by a balance comprising detergent additive components. The laundry detergent composition according to. 16. The composition is in tablet form, preferably the binder is characterized by a hydrotrope having a first polar group and a second polar group separated from each other by at least 5 aliphatic carbon atoms. A tablet detergent composition is characterized by a binder characterized in that the binder further comprises a non-gelling binder, and even more preferably the non-gelling binder is Polyethylene glycol having a molecular weight of 1000 to 4000, preferably with a non-gelling binder to hydrotrope ratio of 2: 1 to 60: 1, preferably 3: 1 to 30: 1, more preferably 3: 1 to 15
The laundry detergent composition according to any one of claims 1 to 15, wherein the laundry detergent composition is 1: 1. 17. The detergent tablet according to claim 16, wherein the operating window of the detergent tablet is spread with a hydrotrope.