DE60032164T2 - DETERGENT WASHING ADDITIVE - Google Patents

Description

TECHNICAL TERRITORY

The The present invention relates to laundry detergent compositions, containing a semi-polar nonionic surfactant and certain polymer, Cyclomerol based oligomer or copolymer materials and others Detergent components, including a builder compound.

BACKGROUND THE INVENTION

It It is well known that changing cycles of use and washing of fabrics and textiles, such as worn garments and Clothing, the look and integrity of the so used and washed Fabric and textile articles inevitably affect. Fabrics and textiles are used over time and when used just off. The washing of fabrics and textiles is necessary to remove dirt and stains during the ordinary Use in it and accumulate on it to remove. The washing process however, you can over many cycles worsening the integrity and appearance of such Reinforce fabrics and textiles and contribute to it.

A Deterioration of tear strength and the appearance of fabrics can appear in different ways to step. Short fibers are made by the mechanical washing process made of woven and knitted fabric / textile structures. These dissolved Fibers can Lint, fringe or "pills" that form on the surface of substances are visible and the appearance of novelty of the substance reduce. Furthermore can be repeated washing of fabrics and textiles, especially with bleach-containing washing products, dyes from fabrics and Remove textiles and as a result of reduced color intensity, and in many cases as a result of changes in shades and shades, give a faded, worn look.

In In view of the above, several materials were used, the laundry detergent products added could become and with the fibers of those washed with such detergent products Fabrics and textiles combine and thereby the tendency of the washed ones Reduce fabrics / textiles to a deterioration of their appearance or minimize identified in the department. Examples of such materials are cationic softening surfactants, cycloamine-based polymers, dye transfer inhibitors, Complexing agent, crystal growth inhibitor. Cycloamine-based polymers are disclosed, for example, as fabric care agents in WO-A-98/17762.

however It was found that the cationic fabric care polymers on Cycloamine based not particularly compatible with the high concentrations anionic surfactants that are normally in the conventional Laundry detergent compositions are formulated. It was further found that these anionic Surfactants significantly increase the efficiency of such cycloamine-based compounds reduce. Such high concentrations of anionic surfactants become normally used to provide good cleaning properties. To compositions with such cationic polymers based on cycloamine To formulate, therefore, detergent compositions without anionic Surfactants, but formulated with nonionic surfactants. However, that became found that detergent compositions with a high concentration of nonionic Surfactants do not offer the same cleaning performance as comparable high concentrations of anionic surfactants and harder to formulate are, especially at high electrolyte content.

In In view of the above, the object of the present invention therefore, a laundry detergent composition to formulate the excellent cleaning properties together with excellent textile care benefits. It was surprisingly found that the combination of a semi-polar nonionic Surfactant with the above-mentioned cationic polymer based on cycloamine both excellent cleaning properties as well as excellent fabric care benefits offers.

It It was also found that the combination of the semi-polar nonionic surfactants with the cycloamine based polymers present invention good inhibition of dye transfer and provides protection against fading.

Furthermore It was found that the compositions of the present Invention show a high physical stability when in one liquid Form are formulated.

TECHNICAL BACKGROUND

DE-A-2750777 discloses foam bath compositions that are semi-polar nonionic Surfactants such as amine oxides and cationic, nitrogen-containing polymers contained by cyclic units containing two nitrogen atoms are derived. US-A-3917817 and US-A-4013787 disclose hair treatment compositions, z. As shampoos, the piperazine-based film-forming polymers and in some cases also contain amine oxide surfactants. WO-A-98/17762 discloses polycationic Condensation products based on piperazines, imidazoles and their derivatives in combination with nonionic surfactants in detergent compositions, which are preferably free of anionic surfactants, and in "aftertreatment agents" for textiles.

SUMMARY THE INVENTION

The The present invention is directed to laundry detergent compositions which are free of anionic surfactants and a semi-polar, nonionic surfactant, a polymer, oligomer or copolymer Include cycloamine base. Such compositions provide good cleaning performance as well as the desired Benefits for Appearance and integrity of textiles. The polymer, oligomer or cycloamine-based copolymer is represented by the following formula characterized as defined below.

In In its method aspect, the present invention relates to washing of fabrics and textiles in aqueous Washing or treatment solutions, from effective amounts of the detergent compositions herein are formed or formed from the individual components of these compositions are. The washing of fabrics and textiles in such washing solutions, followed by rinsing and drying, imparts the fabric and textile articles thus treated Advantages in terms of fabric cleaning as well as the appearance of the substance. Such fabric care benefits can be improved overall Appearance, reduction of nodule / lint, Fading protection, improved dye transfer inhibition, improved wear resistance and / or improved softness.

DETAILED DESCRIPTION OF THE INVENTION

The Laundry detergent compositions of the present invention are free of anionic surfactants and include a cycloamine-based polymer and an amine oxide surfactant and offer excellent cleaning properties along with excellent Fabric care benefits. The compositions also contain conventional ones Laundry detergent components, as defined in claim 1.

Without To be bound by theory, it is believed that the semipolar nonionic surfactants of their chemical property after a certain "hidden" anionic property introduce. Therefore, these semi-polar nonionic surfactants offer good Cleaning properties while they are do not interact with the cationic polymers, making them outstanding Textile cleaning and textile care properties offer.

moreover was also surprisingly found that such semi-polar nonionic surfactants within the compositions of the present invention as hydrotropes Substances act when formulated in liquid form. Without wishing to be bound by theory, it is indeed true In the prior art that high concentrations of nonionic Surfactants in liquid Compositions lead to phase separation. It was determined, that the semi-polar nonionic surfactants of the present invention act as hydrotrope substances and significantly reduce phase separation. It was therefore found that these are semi-polar nonionic Surfactants is the formulation of high nonionic detergent compositions simplify and increase the physical stability of liquid products. This allows the formulation of laundry detergent compositions, which comprise a high concentration of nonionic surfactants and which are perfectly fluid isotropic liquids.

The first basic element of laundry detergent compositions The present invention is the polymer, oligomer or copolymer based on cycloamine, as described below:

A) polymer, oligomer or cycloamine-based copolymer materials

at the first basic ingredient of the compositions of the present invention This invention is one or more polymers, oligomers or copolymers based on cycloamine. It has been shown that such Materials fabrics and textiles washed in aqueous washing solutions which are formed from detergent compositions, the contain such cycloamine-based fabric treatment materials, give a number of advantages in terms of appearance. These For example, total benefits can be gained in terms of appearance improved appearance of the washed fabrics, reduction of the formation of pills or lint, improved dye transfer inhibition, Protection against color fading, improved abrasion resistance etc. include.

As mentioned above, may be the combination of semi-polar nonionic surfactants with in the compositions of the invention and methods used cycloamine-based fabric treatment agents such benefits for Provide the appearance of the fabrics while having a good cleaning performance is maintained.

Of the Polymer, oligomer or copolymer composition component Cycloamine base herein may be combinations of these based on cycloamine Materials include. For example, a mixture of piperidine and epihalohydrin condensates with a mixture of morpholine and epihalohydrin condensates combined to the desired To achieve fabric treatment results. In addition, the molecular weight the cycloamine-based fabric treatment agent within the mixture vary as shown in the examples below.

As Experts know, an oligomer is a molecule that consists of only a few Monomer units persists while Include polymers significantly more monomer units. For the present Invention are oligomers as molecules with an average Molecular weight is defined below about 1,000 and polymers are molecules with one average molecular weight greater than about 1,000. copolymers are polymers or oligomers wherein two or more different Monomers were polymerized simultaneously or sequentially. copolymers of the present invention For example, include polymers or oligomers derived from a mixture from a monomer based on a primary cycloamine monomer, e.g. B. Piperidine, and a secondary one Cycloamine monomer, z. As morpholine, polymerized.

The Textile treatment component of the detergent compositions herein generally from 0.01% to 5% by weight. on the detergent composition, preferably a proportion of 0.1% to 4% by weight, more preferably 0.75% to 3 %.

• worin:
• – jedes T unabhängig ausgewählt ist aus der Gruppe, bestehend aus H, C₁-C₁₂-Alkyl, substituiertem Alkyl, C₇-C₁₂-Alkylaryl,
  
• – worin W mindestens einen cyclischen Bestandteil umfasst, ausgewählt aus der Gruppe, bestehend aus:
  
  zusätzlich zu dem mindestens einen cyclischen Bestandteil kann W auch eine aliphatische oder substituierte aliphatische Einheit der folgenden allgemeinen Struktur umfassen:
  
• – jedes B ist unabhängig C₁-C₁₂-Alkylen, substituiertes C₁-C₁₂-Alkylen, C₃-C₁₂-Alkenylen, C₈-C₁₂-Dialkylarylen, C₈-C₁₂-Dialkylarylendiyl und (R₅O)_nR₅;
• – jedes D ist unabhängig C₂-C₆-Alkylen;
• – jedes Q ist unabhängig ausgewählt aus der Gruppe, bestehend aus Hydroxy, C₁-C₁₈-Alkoxy, C₂-C₁₈-Hydroxyalkoxy, Amino-, C₁-C₁₈-Alkylamino-, -Dialkylamino-, -Trialkylaminogruppen, heterocyclischen Monoaminogruppen und Diaminogruppen;
• – jedes R₁ ist unabhängig ausgewählt aus der Gruppe, bestehend aus H, C₁-C₈-Alkyl und C₁-C₈-Hydroxyalkyl;
• – jedes R₂ ist unabhängig ausgewählt aus der Gruppe, bestehend aus C₁-C₁₂-Alkylen, C₁-C₁₂-Alkenylen, -CH₂-CH(OR₁)-CH₂, C₈-C₁₂-Alkarylen, C₄-C₁₂-Dihydroxyalkylen, Poly-(C₂-C₄-Alkylenoxy)alkylen, H₂CH(OH)CH₂OR₂OCH₂CH(OH)CH₂- und C₃-C₁₂-Kohlenwasserstoffeinheiten; mit der Maßgabe, dass, wenn R₂ eine C₃-C₁₂-Kohlenwasserstoffeinheit ist, die Kohlenwasserstoffeinheit 2 bis 4 Verzweigungseinheiten der folgenden allgemeinen Struktur umfassen kann:
  
• – jedes R₃ ist unabhängig ausgewählt aus der Gruppe, bestehend aus H, R₂, O, C₁-C₂₀-Hydroxyalkyl, C₁-C₂₀-Alkyl, substituiertem Alkyl, C₆-C₁₁-Aryl, substituiertem Aryl, C₇-C₁₁-Alkylaryl, C₁-C₂₀-Aminoalkyl,
  
  Unter den geeigneten Verbindungen der vorliegenden Erfindung auf Cycloaminbasis sind die Verbindungen, worin mindestens etwa 10 Mol%, vorzugsweise mindestens etwa 20 Mol%, mehr bevorzugt mindestens etwa 30 Mol% und am meisten bevorzugt mindestens etwa 50 Mol% der R₃-Gruppen O sind, mit der Maßgabe, dass O nur auf einem tertiären N vorliegt. Unter weiteren geeigneten Verbindungen auf Cycloaminbasis der vorliegenden Erfindung sind die Verbindungen, worin:
• – mindestens etwa 1,0 %, vorzugsweise mindestens etwa 5,0 % und mehr bevorzugt mindestens etwa 10 % und am meisten bevorzugt mindestens etwa 20 % der gesamten Anzahl der T- und R₃-Gruppen anionische Einheiten sind, die ausgewählt sind aus der Gruppe, bestehend aus
  
  und Mischungen davon.
• – jedes R₄ ist unabhängig ausgewählt aus der Gruppe, bestehend aus H, C₁-C₂₂-Alkyl, C₁-C₂₂-Hydroxyalkyl, C₁-C₂₂-Aryl und C₇-C₂₂-Alkylaryl;
• – jedes R₅ ist unabhängig ausgewählt aus der Gruppe, bestehend aus C₂-C₈-Alkylen, C₂-C₈-Alkyl, substituiertem Alkylen und A ist ein kompatibles einwertiges oder zwei- oder mehrwertiges Anion; M ist ein kompatibles Kation; b = Zahl, die erforderlich ist, um die Ladung auszugleichen; jedes x ist unabhängig von den anderen 3 bis etwa 1000, vorzugsweise 3 bis 25, mehr bevorzugt 4 bis 20 ist; jedes c ist unabhängig 0 oder 1; jedes h ist unabhängig etwa 1 bis etwa 8; jedes q ist unabhängig 0 bis etwa 6; jedes n ist unabhängig 1 bis etwa 20; jedes r ist unabhängig 0 bis etwa 20 und jedes t ist unabhängig 0 bis 1.

The cycloamine-based polymers, oligomers or copolymers suitable for the purpose of the present invention are characterized by the following general formula:

• wherein:
• Each T is independently selected from the group consisting of H, C ₁ -C ₁₂ alkyl, substituted alkyl, C ₇ -C ₁₂ alkylaryl,
  
• Wherein W comprises at least one cyclic constituent selected from the group consisting of:
  
  In addition to the at least one cyclic constituent, W may also comprise an aliphatic or substituted aliphatic moiety of the following general structure:
  
• Each B is independently C ₁ -C ₁₂ alkylene, substituted C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ alkenylene, C ₈ -C ₁₂ dialkylarylene, C ₈ -C ₁₂ dialkylarylenediyl and (R ₅ O ) _n R ₅ ;
• Each D is independently C ₂ -C ₆ alkylene;
• Each Q is independently selected from the group consisting of hydroxy, C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₈ hydroxyalkoxy, amino, C ₁ -C ₁₈ alkylamino, -dialkylamino, -trialkylamino, heterocyclic Monoamino groups and diamino groups;
• Each R ₁ is independently selected from the group consisting of H, C ₁ -C ₈ alkyl and C ₁ -C ₈ hydroxyalkyl;
• Each R ₂ is independently selected from the group consisting of C ₁ -C ₁₂ -alkylene, C ₁ -C ₁₂ -alkenylene, -CH ₂ -CH (OR ₁ ) -CH ₂ , C ₈ -C ₁₂ -alkarylene, C ₄ -C ₁₂ dihydroxyalkylene, poly (C ₂ -C ₄ alkyleneoxy) alkylene, H ₂ CH (OH) CH ₂ OR ₂ OCH ₂ CH (OH) CH ₂ and C ₃ -C ₁₂ hydrocarbon units; with the proviso that when R _{2 is} a C ₃ -C ₁₂ hydrocarbon moiety, the hydrocarbon moiety may comprise 2 to 4 branching units of the following general structure:
  
• Each R ₃ is independently selected from the group consisting of H, R ₂ , O, C ₁ -C ₂₀ -hydroxyalkyl, C ₁ -C ₂₀ -alkyl, substituted alkyl, C ₆ -C ₁₁ -aryl, substituted aryl, C ₇ -C ₁₁ -alkylaryl, C ₁ -C ₂₀ -aminoalkyl,
  
  Among the suitable cycloamine-based compounds of the present invention are the compounds wherein at least about 10 mole%, preferably at least about 20 mole%, more preferably at least about 30 mole%, and most preferably at least about 50 mole% of the R ₃ groups are O. , with the proviso that O exists only on a tertiary N. Among other suitable cycloamine-based compounds of the present invention are the compounds wherein:
• At least about 1.0%, preferably at least about 5.0% and more preferably at least about 10% and most preferably at least about 20% of the total number of T and R ₃ groups are anionic units selected from Group consisting of
  
  and mixtures thereof.
• Each R ₄ is independently selected from the group consisting of H, C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ hydroxyalkyl, C ₁ -C ₂₂ aryl and C ₇ -C ₂₂ alkylaryl;
• Each R ₅ is independently selected from the group consisting of C ₂ -C ₈ alkylene, C ₂ -C ₈ alkyl, substituted alkylene and A is a compatible monovalent or di- or polyvalent anion; M is a compatible cation; b = number required to balance the charge; each x is independently from the other 3 to about 1000, preferably 3 to 25, more preferably 4 to 20; each c is independently 0 or 1; each h is independently about 1 to about 8; each q is independently 0 to about 6; each n is independently 1 to about 20; each r is independently 0 to about 20 and each t is independently 0 to 1.

These Cycloamine-based polymers can be used be linear or branched. A particular type of branch can be introduced by means of a polyfunctional crosslinking agent. An example for Such a polymer is explained below.

• 1) ein Cycloamin wie Imidazol, Alkylimidazol, Aminoalkylimidazol, Benzimidazol, Piperazin, Aminoalkylpiperazin, Bis(N-aminoalkyl)piperazin, Aminoalkylmorpholin, Aminoalkylpiperidin und optional ein azyklisches Amin und Mischungen davon;
• 2) ein Vernetzungsmittel, ausgewählt aus der Gruppe, bestehend aus 1,2-Dichlorethan, 1,2-Dichlorpropan, 1,3-Dichlorpropan, 1,3-Dichlorpronae-2-ol, 1,4-Dichlorbutan, 1,6-Dichlorhexan, Epichlorhydrin, Bisepoxybutan, Bisglicidylether von 4,4'Didihydroxydiphenyl-dimethylmethan, Bishalohydrine von C2-C8-Diolen, Bisglycidylether von C2-C18-Diolen, Bisglycidylether von Polyalkylenglycolen und Mischungen davon Bevorzugte Verbindungen auf Cycloaminbasis, die in die obige allgemeine Struktur fallen, schließen Verbindungen ein: – worin jedes R₁ für H steht und – mindestens ein W ausgewählt ist aus der Gruppe, bestehend aus:
  

The example section below contains numerous non-limiting examples of cycloamine polymers of the invention.

• 1) a cycloamine such as imidazole, alkylimidazole, aminoalkylimidazole, benzimidazole, piperazine, aminoalkylpiperazine, bis (N-aminoalkyl) piperazine, aminoalkylmorpholine, aminoalkylpiperidine and optionally an acyclic amine and mixtures thereof;
• 2) a crosslinking agent selected from the group consisting of 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,3-dichloroproona-2-ol, 1,4-dichlorobutane, 1,6- Dichlorohexane, epichlorohydrin, bisepoxybutane, bisglicidyl ether of 4,4'-dihydroxydiphenyl-dimethylmethane, bishalohydrins of C2-C8 diols, bisglycidyl ethers of C2-C18 diols, bisglycidyl ethers of polyalkylene glycols, and mixtures thereof Preferred cycloamine-based compounds falling within the above general structure , compounds include: wherein each R _{1 is} H and at least one W is selected from the group consisting of:
  

• – worin jedes R₁ für H steht und
• – mindestens ein W ausgewählt ist aus der Gruppe, bestehend aus:
  

Even more preferred compounds in terms of the appearance and tear resistance of fabrics are those

• Wherein each R _{1 is} H and
• At least one W is selected from the group consisting of:
  

• – worin jedes R₁ für H steht und
• – mindestens ein W ausgewählt ist aus der Gruppe, bestehend aus:
  

And most preferred compounds in terms of the appearance and tear resistance of fabrics are those:

• Wherein each R _{1 is} H and
• At least one W is selected from the group consisting of:
  

Preferred compounds for use as the linker group R ₂ include, but are not limited to: polyepoxides, ethylene carbonate, propylene carbonate, urea, α, β-unsaturated carboxylic acids, esters of α, β-unsaturated carboxylic acids, amides of α, β-unsaturated Carboxylic acids, anhydrides of α, β-unsaturated carboxylic acids, di- or polycarboxylic acids, esters of di- or polycarboxylic acids, amides of di- or polycarboxylic acids, anhydrides of di- or polycarboxylic acids, glycidyl halides, chloroform esters, chloroacetic esters, derivatives of chloroform esters, derivatives of chloroacetic esters , Epihalohydrins, glycerol dichlorohydrins, bis (halohydrins), polyether dihalo compounds, phosgene, polyhalogens, functionalized glycidyl ethers, and mixtures thereof.

In addition, R _{2 may} also comprise a reaction product formed by reacting one or more polyether diamines, alkylenediamines, polyalkylenepolyamines, alcohols, alkylene glycols and polyalkylene glycols with α, β-unsaturated carboxylic acids, esters of α, β-unsaturated carboxylic acids, amides of α, β-unsaturated carboxylic acids and anhydrides of α, β-unsaturated carboxylic acids is formed, with the proviso that the reaction products contain at least two double bonds, two carboxyl groups, two amide groups or two ester groups.

Further preferred cycloamine-based polymer, oligomer or copolymer materials for this purpose Close use Adducts of two or more compositions selected from Group consisting of piperazine, piperidine, imidazole, epichlorohydrin benzyl quat, Epichlorohydrin methyl quat, morpholine and mixtures thereof.

B) The semi-polar nonionic surfactant

The second basic element of the laundry detergent compositions of the present invention is a semi-polar nonionic surfactant, preferably an amine oxide surfactant.

semipolar Nonionic surfactants are a special category of nonionic Surfactants, the water-soluble Amine oxides containing one alkyl moiety of from about 8 to about 18 carbon atoms and 2 units selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides, the one alkyl moiety having from about 8 to about 18 carbon atoms and 2 units selected from the group consisting of alkyl groups and hydroxyalkyl groups with from about 1 to about 3 carbon atoms; and water-soluble sulfoxides, the one alkyl moiety having from about 8 to about 18 carbon atoms and a unit selected from the group consisting of alkyl and hydroxyalkyl units with from about 1 to about 3 carbon atoms.

worin R³ für eine Alkyl-, Hydroxyalkyl- oder Alkylphenylgruppe oder Mischungen davon mit ungefähr 8 bis ungefähr 22 Kohlenstoffatomen steht; R⁴ für eine Alkylen- oder Hydroxyalkylengruppe, die ungefähr 2 bis ungefähr 3 Kohlenstoffatome enthält, oder Mischungen davon steht; x für 0 bis ungefähr 3 steht; und jedes R⁵ eine Alkyl- oder Hydroxyalkylgruppe mit ungefähr 1 bis ungefähr 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit ungefähr 1 bis ungefähr 3 Ethylenoxidgruppen ist. Die R⁵-Gruppen können aneinander gefügt werden, z. B. durch ein Sauerstoff oder Stickstoffatom, um eine Ringstruktur zu bilden.Preferred semi-polar nonionic detergent surfactants for the purpose of the present invention are the amine oxide surfactants having the formula:

wherein R ^{3 is} an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof having from about 8 to about 22 carbon atoms; R ^{4 is} an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is 0 to about 3; and each R ^{5 is} an alkyl or hydroxyalkyl group of about 1 to about 3 carbon atoms or a polyethylene oxide group of about 1 to about 3 ethylene oxide groups. The R ⁵ groups can be joined together, e.g. By an oxygen or nitrogen atom to form a ring structure.

In particular, these amine oxide surfactants include C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides, more preferably the C ₁₂ -C ₁₄ alkyl dimethyl amine oxide.

The Laundry detergent compositions of the present invention generally comprise from 0.1% by weight to 20% by weight, preferably to about 1% by weight to about 10% by weight, more preferably 2% to 7% by weight of such semi-polar nonionic surfactants.

Detergent ingredients

The Laundry detergent compositions of the present invention contain additional detergent components, as defined in claim 1. The exact nature of this extra Component and the degree of their involvement depends on the physical Form of the composition and the type of cleaning process for which they are be used off.

The Laundry detergent compositions of the present invention further comprise a detergent ingredient, selected from nonionic and / or cationic surfactants, polymers or Cellulose based oligomers, dye transfer inhibiting polymers, a mannanase enzyme and / or mixtures thereof.

at Formulation as compositions intended for use in a machine Laundry process are suitable, the compositions of the invention contain both a surfactant as well as a builder compound and additionally a or more detergent components selected from bleaches, additional Enzymes, suds suppressors, Dispersants, lime soap dispersants, soil suspending agents and anti-redeposition agents and anti-corrosion agents. Laundry compositions can be considered as additional Detergent components also contain plasticizer.

The Compositions of the invention may also be used as detergent adjuncts be used. Such additional products are intended to enhance the performance of conventional Add detergent compositions or strengthen.

The Laundry detergent compositions according to the invention can Liquids, Pastes, gels, pieces, Tablets, sprays, foams, Be powder or granules. Granular compositions can also be in "compact" form, and the liquid Compositions can also in a "concentrated" form.

If required is the density of the laundry detergent compositions herein in the range of 400 to 1200 g / liter, preferably 500 to 950 g / liter of composition measured at 20 ° C.

The "compact" form of the compositions herein is best reflected by density and, in terms of composition, the amount of inorganic filler salts: inorganic filler salts are conventional ingredients of powdered detergent compositions; in conventional detergent compositions, the filler salts are present in substantial amounts Rule 17-35% by weight of the total composition In the compact compositions, the filling salt is present in amounts not exceeding 15% by weight of the total composition, preferably 10% by weight, most preferably 5% by weight of the composition The inorganic filler salts as present in the The compositions are selected from the alkali and alkaline earth metal salts of sulfates and chlorides. A preferred bulking salt is sodium sulfate.

Liquid detergent compositions of the invention can also in a "concentrated form" in which Case contain the liquid detergent compositions according to the invention lower compared to conventional liquid detergents Amount of water. As a rule, the water content of the concentrated liquid Detergent preferably less than 40 wt .-%, more preferably less than 30% by weight, most preferably less than 20% by weight the detergent composition.

To the related Use of suitable detergent compounds are selected from the group consisting of the compounds described below.

surfactants

The Laundry detergent compositions of the present invention further comprising other detersive surfactants consisting of anionic, nonionic, zwitterionic, ampholytic or cationic types are selected, or you can contain compatible mixtures of these types.

Preferably include the laundry detergent compositions of the present invention, a high concentration of nonionic Surfactants - one or more - and a low concentration of anionic surfactants - one or more. More preferably, the nonionic surfactants make up the laundry detergent composition a proportion of 1% by weight to 50% by weight of the present invention, most preferably 5% to 30% by weight, more preferably still a proportion of 15% by weight to 25% by weight of the overall composition. More preferably, the anionic ones Surfactants in the laundry detergent compositions a proportion of 0 wt .-% - 10 wt .-% of the present invention, most preferably from 0% to 5% by weight. Even more preferred include the laundry detergent compositions of the present invention are not anionic surfactants.

Preferred nonionic surfactants for the laundry detergent compositions of the present invention are the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide and mixtures thereof. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group of from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. From about 3 to about 7 moles of ethylene oxide, and most preferably 9 to 5 moles of ethylene oxide per mole of alcohol are present in the condensation products. Examples of commercially available nonionic surfactants of this type include Tergitol ^™ 15-S-9 (the condensation product of linear C ₁₁ -C ₁₅ alcohol with 9 moles of ethylene oxide), Tergitol ^™ 24-L-6 NMW (the condensation product of primary C ₁₂ -C ₁₄ -alcohol with 6 moles of narrow molecular weight distribution ethylene oxide) both marketed by Union Carbide; Neodol ^™ 45-9 (the condensation product of linear C ₁₄ -C ₁₅ alcohol with 9 moles of ethylene oxide), Neodol ^™ 23-3 (the condensation product of linear C ₁₂ -C ₁₃ alcohol with 3.0 moles of ethylene oxide), Neodol ^™ 45-7 (the condensation product of C ₁₄ -C ₁₅ alcohol with 7 moles of ethylene oxide), Neodol ^TM 45-5 (the condensation product of C ₁₄ -C ₁₅ alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, Kyro ^TM EOB (the condensation product of C ₁₃ -C ₁₅ alcohol with 9 moles of ethylene oxide) marketed by The Procter & Gamble Company and Genapol LA O 3 O or O 5 O (the condensation product of C ₁₂ -C ₁₄ alcohol with 3 or 5 moles of ethylene oxide), marketed by Hoechst. The preferred range for the HLB value in these products is 8-11 and most preferably 8-10.

Also suitable as the nonionic surfactant of the present invention are alkyl polysaccharides described in U.S. Patent No. 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group, the approximately 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms contains and a polysaccharide, e.g. A hydrophilic polyglycoside group, the approximately 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about Contains 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, for. B. can Exchanged glucose, galactose and galactosyl units for the glucosyl units (Optionally, the hydrophobic group is at the 2, 3, 4 positions etc., which is a glucose or galactose as opposed to a Glucoside or galactoside). The intersaccharide bonds can, for. B. between the 1-position of the additional saccharide units and the 2, 3, 4 and / or 6 positions the preceding saccharide units.

The preferred alkylpolyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _x wherein R ^{2 is} selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0; and x is about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyl polyethoxy alcohol is first formed and then chemically reacted with glucose or a source of glucose to form the glucoside (bond at position 1). The additional glycosyl units can then be attached between their position 1 and the previous glycosyl units at positions 2, 3, 4 and / or 6, preferably above all at position 2.

Also useful as nonionic surfactants are the condensation products of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of about 1500 to about 1800 and is water insoluble. Addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and maintain the liquid character of the product to the point where the polyoxyethylene content accounts for about 50% of the total weight of the condensation product, causing condensation of up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available Plurafac ^™ LF404 and Pluronic ^™ surfactants, marketed by BASF.

Also suitable for use as the nonionic surfactant are the condensation products of ethylene oxide, the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide and generally has a molecular weight of about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product is from about 40% to about 80% Wt .-% polyoxyethylene and has a molecular weight of about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic ^™ compounds marketed by BASF.

worin R¹ H, oder R¹ C_1-4-Hydrocarbyl, 2-Hydroxyethyl, 2-Hydroxypropyl oder eine Mischung davon ist, R² C_5-31-Hydrocarbyl ist und Z ein Polyhydroxyhydrocarbyl mit einer linearen Hydrocarbylkette mit mindestens 3 Hydroxylen, die direkt mit der Kette verbunden sind, oder ein alkoxyliertes Derivat davon ist. Vorzugsweise ist R¹ Methyl, R² ist eine gerade C_11-15-Alkyl- oder C_16-18-Alkyl- oder -Alkenylkette, wie Kokosnussalkyl, oder Mischungen davon, und Z ist in einer reduktiven Aminierung von einem reduzierenden Zucker, wie Glucose, Fructose, Maltose, Lactose, abgeleitet.Other useful nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:

wherein R ^{1 is} H, or R ^{1 is} C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ^{2 is} C _5-31 hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls, which are directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R ^{1 is} methyl, R ² is a straight C _11-15 alkyl or C _16-18 alkyl or alkenyl chain, such as coconut alkyl, or mixtures thereof, and Z is in a reductive amination of a reducing sugar, such as Glucose, fructose, maltose, lactose, derived.

Further nonionic surfactants are polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols, the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount of from about 2 to about 25 moles, more preferably from about 3 to about 15 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ^™ CO-630, available from GAF Corporation; and Triton ^™ X-45, X-114, X-100 and X-102, all available from the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as the alkyltrimethylammonium halides and those surfactants having the formula: [R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X wherein R ^{2 is} an alkyl or alkylbenzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R ^{3 is} selected from the group consisting from -CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) -, -CH ₂ CH (CH ₂ OH) -, -CH ₂ CH ₂ CH ₂ - and mixtures thereof; each R ^{4 is} selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl ring structures formed by joining the two R ⁴ groups, -CH ₂ CHOH-CHOHCOR ⁶ CHOHCH ₂ OH, wherein R ^{6 is} any hexose or hexose polymer of molecular weight less than about 1000, and hydrogen when y is not 0; R ⁵ is R ⁴ or an alkyl chain, wherein the total number of carbon atoms of R ² plus R ^{5 is} not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

worin R1 ein kurzkettiges Alkyl(C6-C10) oder Alkylamidoalkyl der Formel (II) ist:

y ist 2–4, vorzugsweise 3.
worin R2 H oder ein C1-C3-Alkyl ist,
worin x 0–4, vorzugsweise 0–2, am meisten bevorzugt 0 ist,
worin R3, R4 und R5 entweder gleich oder verschieden sind und entweder ein kurzkettiges Alkyl(C1-C3) oder alkoxyliertes Alkyl der Formel III sein können,
worin X^– ein Gegenion ist, vorzugsweise ein Halogenid, z. B. Chlorid oder Methylsulfat.

R6 ist C₁-C₄, und z ist 1 oder 2.Quaternary ammonium surfactant suitable for the present invention has the formula (I):

wherein R 1 is a short-chain alkyl (C 6 -C 10) or alkylamidoalkyl of the formula (II):

y is 2-4, preferably 3.
wherein R 2 is H or a C 1 -C 3 -alkyl,
wherein x is 0-4, preferably 0-2, most preferably 0,
wherein R3, R4 and R5 are either the same or different and may be either a short chain alkyl (C1-C3) or alkoxylated alkyl of formula III,
wherein X ^{- is} a counterion, preferably a halide, e.g. As chloride or methyl sulfate.

R6 is C ₁ -C ₄ , and z is 1 or 2.

Preferred quaternary ammonium surfactants are those as defined in formula I wherein
R _{1 is} C ₈ , C ₁₀ or mixtures thereof, x = o,
R ₃ , R ₄ = CH ₃ and R ₅ = CH ₂ CH ₂ OH.

Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula: R ₁ R ₂ R ₃ R ₄ N ⁺ X (i) wherein R _{1 is} C ₈ -C ₁₆ -alkyl, R ₂ , R ₃ and R ₄ are each independently C ₁ -C ₄ -alkyl, C ₁ -C ₄ -hydroxyalkyl, benzyl and - (C ₂ H ₄₀ ) _x H in which x has a value of 2 to 5 and X is an anion. Not more than one of R ₂ , R ₃ or R ₄ should be benzyl.

The preferred alkyl chain length for R ₁ is C ₁₂ -C ₁₅ , especially when the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat, or derived synthetically by olefin build up or OXO alcohol synthesis. Preferred groups for R ₂ R ₃ and R ₄ are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulfate, acetate and phosphate ions.

Examples of suitable quaternary ammonium compounds of formula (i) for use herein are:
Coconut trimethyl ammonium chloride or bromide;
Coconut methyldihydroxyethylammonium chloride or bromide;
decyl triethyl ammonium chloride;
Decyldimethylhydroxyethylammonium chloride or bromide;
C _12-15 dimethylhydroxyethyl ammonium chloride or bromide;
Coconut dimethyl hydroxyethyl ammonium chloride or bromide;
Myristyltrimethylammoniummethylsulphat;
Lauryldimethylbenzylammonium chloride or bromide;
Lauryldimethyl (ethenoxy) _4- ammonium chloride or bromide;
Choline esters (compounds of formula (i) wherein R ₁

Other cationic surfactants useful herein are also disclosed in U.S. Patent No. 4,228,044, Cambre, issued October 14, 1980, and in the European patent application EP 000,224 described.

Other cationic materials are the fabric softening ingredients, including water quaternary Ammonium fabric softening agent or its corresponding amine precursor, wherein the most common Ammonium chloride with two long alkyl chains or methyl sulfate.

• 1) Ditalgdimethylammoniumchlorid (DTDMAC);
• 2) dihydriertes Talgdimethylammoniumchlorid;
• 3) dihydriertes Talgdimethylammoniummethylsulfat;
• 4) Distearyldimethylammoniumchlorid;
• 5) Dioleyldimethylammoniumchlorid;
• 6) Dipalmitylhydroxyethylmethylammoniumchlorid;
• 7) Stearylbenzyldimethylammoniumchlorid;
• 8) Talgtrimethylammoniumchlorid;
• 9) hydriertes Talgtrimethylammoniumchlorid;
• 10) C_12-14-Alkylhydroxyethyldimethylammoniumchlorid;
• 11) C_12-18-Alkyldihydroxyethylmethylammoniumchlorid;
• 12) Di(stearoyloxyethyl)dimethylammoniumchlorid (DSOEDMAC);
• 13) Di(talgoxyethyl)dimethylammoniumchlorid;
• 14) Ditalgimidazoliniummethylsulfat;
• 15) 1-(2-Talgamidoethyl)-2-talgimidazoliniummethylsulfat.

Preferred cationic softening agents include the following:

• 1) Ditallow dimethyl ammonium chloride (DTDMAC);
• 2) dihydrogenated tallow dimethyl ammonium chloride;
• 3) dihydrogenated tallow dimethyl ammonium methyl sulfate;
• 4) distearyldimethylammonium chloride;
• 5) dioleyldimethylammonium chloride;
• 6) dipalmitylhydroxyethylmethylammonium chloride;
• 7) stearylbenzyldimethylammonium chloride;
• 8) tallow trimethyl ammonium chloride;
• 9) hydrogenated tallow trimethyl ammonium chloride;
• 10) C _12-14 -alkylhydroxyethyldimethylammonium chloride;
• 11) C _12-18 alkyldihydroxyethylmethylammonium chloride;
• 12) di (stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);
• 13) di (tallowoxyethyl) dimethylammonium chloride;
• 14) ditallowimidazolinium methylsulfate;
• 15) 1- (2-tallowamidoethyl) -2-tallowimidazolinium methylsulfate.

biological degradable quaternary Ammonium compounds have been used as alternatives to the traditional ones Ammonium chlorides with two long alkyl chains and methyl sulfates presents. Such quaternary Ammonium compounds contain long-chain alk (en) yl groups which are interrupted by functional groups such as carboxy groups. The materials and fabric softening compositions containing these are numerous publications, such as EP-A-0,040,562 and EP-A-0,239,910, disclosed.

worin Q ausgewählt ist aus -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR⁴-C(O)-, -C(O)-NR⁴-;
R¹ ist (CH₂)_n-Q-T² oder T³;
R² ist (CH₂)_m-Q-T⁴ oder T⁵ oder R³;
R³ ist C₁-C₄-Alkyl oder C₁-C₄-Hydroxyalkyl oder H;
R⁴ ist H oder C₁-C₄-Alkyl oder C₁-C₄-Hydroxyalkyl;
T¹, T², T³, T⁴, T⁵ sind unabhängig voneinander C₁₁-C₂₂-Alkyl oder -Alkenyl;
n und m sind ganze Zahlen von 1 bis 4; und
X^– ist ein Weichmacher-verträgliches Anion. Nicht einschränkende Beispiele für Weichmacher-verträgliche Anionen umfassen Chlorid oder Methylsulfat.The quaternary ammonium compounds and amine precursors herein have the formula (I) or (II) below:

wherein Q is selected from -OC (O) -, -C (O) -O-, -OC (O) -O-, -NR ⁴ -C (O) -, -C (O) -NR ⁴ -;
R ¹ is (CH ₂ ) _n -QT ² or T ³ ;
R ² is (CH ₂ ) _m -QT ⁴ or T ⁵ or R ³ ;
R ³ is C ₁ -C ₄ -alkyl or C ₁ -C ₄ -hydroxyalkyl or H;
R ⁴ is H or C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl;
T ¹ , T ² , T ³ , T ⁴ , T ⁵ are independently C ₁₁ -C ₂₂ alkyl or alkenyl;
n and m are integers from 1 to 4; and
X ^- is a plasticizer-compatible anion. Non-limiting examples of plasticizer-compatible anions include chloride or methyl sulfate.

The alkyl or alkenyl chain T ¹ , T ² , T ³ , T ⁴ , T ⁵ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain can be straight or branched. Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material. The compounds wherein T ¹ , T ² , T ³ , T ⁴ , T ^{5 is} the mixture of long chain materials typical of tallow are particularly preferred.

Specific examples of quaternary ammonium compounds suitable for use in the subject aqueous fabric softening compositions include:
N, N-di (tallowyloxyethyl) -N, N-dimethyl ammonium chloride;
N, N-di (canolyloxy-ethyl) -N, N-dimethyl ammonium chloride;
N, N-di (tallowyloxyethyl) -N-methyl, N- (2-hydroxyethyl) ammonium chloride;
N, N-di (canolyloxy-ethyl) -N-methyl, N- (2-hydroxyethyl) ammonium chloride;
N, N-di (2-tallowyloxy-2-oxoethyl) -N, N-dimethyl ammonium chloride;
N, N-di (2-canolyloxy-2-oxoethyl) -N, N-dimethyl ammonium chloride
N, N-di (2-tallowyloxyethylcarbonyloxyethyl) -N, N-dimethyl ammonium chloride;
N, N-di (2-canolyloxyethylcarbonyloxyethyl) -N, N-dimethyl ammonium chloride;
N- (2-tallowoyloxy-2-ethyl) -N- (2-tallowyloxy-2-oxoethyl) -N, N-dimethyl ammonium chloride;
N- (2-canolyloxy-2-ethyl) -N- (2-canolyloxy-2-oxo-ethyl) -N, N-dimethyl ammonium chloride;
N, N, N-tri (tallowyloxyethyl) -N-methyl ammonium chloride;
N, N, N-tri (canolyloxy-ethyl) -N-methyl ammonium chloride;
N- (2-tallowoyloxy-2-oxoethyl) -N- (tallowyl) -N, N-dimethyl ammonium chloride;
N- (2-canolyloxy-2-oxoethyl) -N- (canolyl) -N, N-dimethyl ammonium chloride;
1,2-Ditallowyloxy-3-N, N, N-trimethylammoniopropane chloride; and
1,2-dicanolyloxy-3-N, N, N-trimethylammoniopropane chloride;
and mixtures of the above active ingredients.

at Included herein are the laundry detergent compositions of the present invention typically from 0.2% to about 25% by weight, preferably about 1% by weight to about 8 wt .-% of such cationic surfactants.

conventional suitable anionic surfactants themselves can be several different Types belong. For example, are water-soluble Salts of the higher fatty acids, d. H. "Soaps", suitable anionic surfactants in the compositions herein. This includes alkali metal soaps, like the sodium, potassium, ammonium and alkyl ammonium salts of higher fatty acids, the from about 8 to about 24 carbon atoms, and preferably about 12 contain up to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Especially useful are the sodium and potassium salts of the mixtures of coconut oil and tallow derived fatty acids, d. H. Sodium or potassium tallow and coconut soap.

Other anionic surfactants which are not soaps and which are suitable for use herein include the water-soluble salts, preferably the alkali metal and ammonium salts, of the organic Sulfur reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfuric acid or sulfuric acid ester group. (The term "alkyl" includes the alkyl moiety of acyl groups.) Examples of this group of synthetic surfactants are a) the sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C ₈ -C ₁₈ carbon atoms). b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates, especially those in which the alkyl group contains from 10 to 22, preferably from 12 to 18, carbon atoms and in which and (c) the sodium and potassium alkylbenzenesulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms in straight or branched chain configuration, for example those of the type described in US Pat. Nos. 2,220,099 and 2,477,383.) Especially valuable are linear, straight-chain alkyl benzene sulfonates in which the average the number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C _11-13 LAS.

worin R₁ eine C₆-C₁₂-Alkylgruppe ist; n von etwa 2 bis etwa 4 ist, X eine Überbrückungsgruppe ist, die von NH, CONH, COO oder O ausgewählt ist, oder X abwesend sein kann; und R₃ und R₄ individuell ausgewählt sind von H, C₁-C₄-Alkyl oder (CH₂-CH₂-O(R₅)), worin R₅ H oder Methyl ist. Besonders bevorzugte Tenside auf Aminbasis schließen die folgenden ein:

worin R₁ eine C₆-C₁₂-Alkylgruppe ist und R₅ H oder CH₃ ist. Besonders bevorzugte Amine zum Gebrauch in den oben stehend definierten Tensiden schließen diejenigen ein, die ausgewählt sind aus der Gruppe, bestehend aus Octylamin, Hexylamin, Decylamin, Dodecylamin, C₈-C₁₂-Bis(hydroxyethyl)amin, C₈-C₁₂-Bis(hydroxyisopropyl)amin, C₈-C₁₂-Amido-propyldimethylamin oder Mischungen davon. In einer äußert bevorzugten Ausführungsform ist das Tensid auf Aminbasis mit der folgenden Formel beschrieben: R₁-C(O)-NH-(CH₂)₃-N(CH₃)₂, worin R₁ C₈-C₁₂-Alkyl ist.Other suitable surfactants for use in the laundry detergent compositions described herein are amine-based surfactants of the following general formula:

wherein R _{1 is} a C ₆ -C ₁₂ alkyl group; n is from about 2 to about 4, X is a bridging group selected from NH, CONH, COO or O, or X may be absent; and R ₃ and R _{4 are} individually selected from H, C ₁ -C ₄ alkyl or (CH ₂ -CH ₂ -O (R ₅ )) wherein R _{5 is} H or methyl. Particularly preferred amine-based surfactants include the following:

wherein R _{1 is} a C ₆ -C ₁₂ alkyl group and R _{5 is} H or CH ₃ . Particularly preferred amines for use in the above-defined surfactants include those selected from the group consisting of octylamine, hexylamine, decylamine, dodecylamine, C ₈ -C ₁₂ bis (hydroxyethyl) amine, C ₈ -C ₁₂ - Bis (hydroxyisopropyl) amine, C ₈ -C ₁₂ amido-propyldimethylamine or mixtures thereof. In an even more preferred embodiment, the amine-based surfactant is described by the formula: R ₁ -C (O) -NH- (CH ₂ ) ₃ -N (CH ₃ ) ₂ wherein R _{1 is} C ₈ -C ₁₂ alkyl ,

Polymer or oligomer on cellulose basis

The laundry detergent compositions of the present invention may further comprise one or more of comprise a plurality of cellulose-based polymers or oligomers. These materials have been found to impart a number of appearance benefits to fabrics and textiles laundered in aqueous wash solutions formed from detergent compositions containing such cellulosic-based fabric treatment materials. These appearance benefits may include, for example, an overall improved appearance of the fabrics being washed, a reduction in the formation of pills or lint, protection against color fading, improved abrasion resistance, and the like.

One suitable type of polymer or oligomer textile treatment material Cellulosic for use herein has an average Molecular weight of about 5,000 to about 2,000,000, preferably from about 50,000 to about 1,000,000.

These Cellulose-based compounds generally account for a proportion from 0.1% to 5% by weight, more preferably 0.5% Wt .-% to 4 wt .-%, more preferably a share of 0.75 wt .-% to 3% by weight of the detergent composition.

worin jedes R ausgewählt ist aus der Gruppe, bestehend aus R₂, R_C und

worin:

• – jedes R₂ unabhängig ausgewählt ist aus der Gruppe, bestehend aus H und C₁-C₄-Alkyl;
  
  worin jedes Z unabhängig ausgewählt ist aus der Gruppe, bestehend aus M, R₂, R_C und R_H;
• – jedes R_H unabhängig ausgewählt ist aus der Gruppe, bestehend aus C₅-C₂₀-Alkyl, C₅-C₇-Cycloalkyl, C₇-C₂₀-Alkylaryl, C₇-C₂₀-Arylalkyl, substituiertem Alkyl, Hydroxyalkyl, C₁-C₂₀-Alkoxy-2-hydroxyalkyl, C₇-C₂₀-Alkylaryloxy-2-hydroxyalkyl, (R₄)₂N--Alkyl, (R₄)₂-N-2-Hydroxyalkyl, (R₄)₃N--Alkyl, (R₄)₃-N-2-Hydroxyalkyl, C₆-C₁₂-Aryloxy-2-hydroxyalkyl,
  
• – jedes R₄ unabhängig ausgewählt ist aus der Gruppe, bestehend aus H, C₁-C₂₀-Alkyl, C₅-C₇-Cycloalkyl, C₇-C₂₀-Alkylaryl, C₇-C₂₀-Arylalkyl, Aminoalkyl, Alkylaminoalkyl, Dialkylaminoalkyl, Piperidinoalkyl, Morpholinoalkyl, Cycloalkylaminoalkyl und Hydroxyalkyl;
• – jedes R₅ unabhängig ausgewählt ist aus der Gruppe, bestehend aus H, C₁-C₂₀-Alkyl, C₅-C₇-Cycloalkyl, C₇-C₂₀-Alkylaryl, C₇-C₂₀-Arylalkyl, substituiertem Alkyl, Hydroxyalkyl, (R₄)₂N--Alkyl und (R₄)₃N--Alkyl; worin: M ein geeignetes Kation ausgewählt aus der Gruppe, bestehend aus Na, K, 1/2 Ca und 1/2 Mg, ist; jedes x von 0 bis etwa 5 ist; jedes y von etwa 1 bis etwa 5 ist und vorausgesetzt, dass:
• – der Substitutionsgrad für Gruppe R_H zwischen etwa 0,001 und 0,1 liegt, mehr bevorzugt zwischen etwa 0,005 und 0,05 und am meisten bevorzugt zwischen etwa 0,01 und 0,05;
• – der Substitutionsgrad der Gruppe R_C, worin Z für H oder M steht, zwischen etwa 0,2 und 2,0, mehr bevorzugt zwischen etwa 0,3 und 1,0 und am meisten bevorzugt zwischen etwa 0,4 und 0,7 liegt;
• – jedes R_H mit einer positiven Ladung durch ein geeignetes Anion ausgeglichen wird und
• – zwei R₄ auf demselben Stickstoff zusammen eine Ringstruktur bilden können, die ausgewählt ist aus der Gruppe, bestehend aus Piperidin und Morpholin.

A suitable group of cellulosic polymer or oligomer materials for use herein is characterized by the following formula:

wherein each R is selected from the group consisting of R ₂ , R _C and

wherein:

• Each R _{2 is} independently selected from the group consisting of H and C ₁ -C ₄ alkyl;
  
  wherein each Z is independently selected from the group consisting of M, R ₂ , R _C and R _H ;
• Each R _{H is} independently selected from the group consisting of C ₅ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl, hydroxyalkyl, C ₁ -C ₂₀ alkoxy-2-hydroxyalkyl, C ₇ -C ₂₀ -Alkylaryloxy-2-hydroxyalkyl, (R _{4) 2} N - alkyl, (R _{4) 2} N-2-hydroxyalkyl, (R _{4) 3} N-alkyl, (R ₄ ) ₃ -N-2-hydroxyalkyl, C ₆ -C ₁₂ -aryloxy-2-hydroxyalkyl,
  
• Each R _{4 is} independently selected from the group consisting of H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, aminoalkyl, alkylaminoalkyl , Dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl;
• Each R _{5 is} independently selected from the group consisting of H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl, Hydroxyalkyl, (R ₄ ) ₂ N - alkyl and (R ₄ ) ₃ N - alkyl; wherein: M is a suitable cation selected from the group consisting of Na, K, 1/2 Ca and 1/2 Mg; each x is from 0 to about 5; each y is from about 1 to about 5, and provided that:
• The degree of substitution for group R _{H is} between about 0.001 and 0.1, more preferably between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05;
• The degree of substitution of the group R _C , wherein Z is H or M, is between about 0.2 and 2.0, more preferably between about 0.3 and 1.0, and most preferably between about 0.4 and 0.7 lies;
• - Each R _{H is} balanced with a positive charge by a suitable anion and
• - Two R ₄ on the same nitrogen together can form a ring structure which is selected from the group consisting of piperidine and morpholine.

The "degree of substitution" for group R _H , sometimes abbreviated herein as "DS _RH ", means the number of moles of components of the group R _H substituted per anhydrous glucose unit, where an anhydrous glucose unit is a six-membered ring, as described in U.S. Pat of the repeating unit of general structure shown above.

The "degree of substitution" for group R _C , which is sometimes abbreviated herein as "DS _RC ", means the number of moles of group R _C components wherein Z is H or M substituted per anhydrous glucose unit, an anhydrous glucose unit being a six membered ring is as shown in the basic unit of the above general structure. The requirement that Z is H or M is necessary to ensure that a sufficient number of carboxymethyl groups are present so that the resulting polymer is soluble. It will be understood that, in addition to the required number of R _C moieties, wherein Z is H or M, further R _C moieties may be present, and most preferably, wherein Z is a group other than H or M.

Detergent Builder

The Laundry detergent compositions herein can and also at 0.1% to 80% by weight of a detergent builder include. Preferably, these compositions comprise in liquid form from about 1% to 10% by weight of the builder component. Preferably comprise these compositions in granular form of about 1% by weight to 50% by weight of the builder component. Detergent builders are known in the art and include, for example Phosphate salts as well as various organic and inorganic Non-phosphorus builder.

Water-soluble, Non-phosphorus organic builders useful herein include various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulphonates. Examples for polyacetate and polycarboxylate builders are the sodium, potassium, lithium, Ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid Benzolpolycarboxylatsäuren and Citric acid. Other suitable polycarboxylates for use herein are the polyacetal carboxylates, U.S. Patent No. 4,144,226, issued March 13, 1979 to Crutchfield et al., and U.S. Patent No. 4,246,495 issued Mar. 27, 1979 to Crutchfield et al. are described. Particularly preferred polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions, a combination of tartrate monosuccinate and tartrate disuccinate and issued in U.S. Patent No. 4,663,071, Bush et al on May 5, 1987.

Examples of suitable inorganic non-phosphorus builders include the silicates, aluminosilicates, borates, and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate and silicates having a weight ratio SiO ₂ to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Also preferred are aluminosilicates, including zeolites. Such materials and their use as detergent builders are more fully described in Corkill et al., U.S. Patent No. 4,605,509. Also described in U.S. Patent No. 4,605,509 are crystalline layered silicates which are suitable for use in the detergent compositions of this invention.

Optional detergent ingredients

The Laundry detergent compositions of the present invention also any number of additional ones include optional ingredients. These include conventional ones Ingredients of detergent compositions, such as enzymes and Enzyme stabilizers, foam boosters or suds suppressors, anti-tarnish and corrosive agents, bleaching agents, soil suspending agents, soil release agents, germicidal Means, pH regulator, alkalinity, which are not builders, complexing agents, organic and inorganic fillers, Solvent, hydrotropic compounds, optical brighteners, dye transfer inhibitors, Dyes and perfumes.

pH regulator can be necessary in certain applications where the pH of the wash solution is greater than is about 10.0, because the benefits of textile integrity are defined Compositions at a higher pH begins to decrease. Therefore, if the washing solution after the addition of the cycloamine-based polymer, oligomer or copolymer material higher than is about 10.0, a pH regulator should be used to adjust the pH the washing solution to lower than about 10.0, preferably to a pH less than about 9.5, and most preferably less than about 7.5. suitable pH regulators are known to those skilled in the art.

preferred optional ingredients for include inclusion in the detergent compositions herein a bleach, e.g. A peroxygen bleach. These peroxygen bleaches can be organic or inorganic nature. Inorganic peroxygen bleach become common used in combination with a bleach activator.

suitable organic peroxygen bleaches include percarboxylic acid bleaches and Salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, Magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioc one. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman on November 20, 1984, European Patent Application EP-A-133,354, Banks et al., published on February 20, 1985, and in U.S. Patent 4,412,934, Chung et al on November 1, 1983, disclosed. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA), as in U.S. Patent 4,634,551 issued January 6, 1987 to Burns et al.

inorganic Peroxygen bleaches, generally in particulate form, may also be used in the detergent compositions herein. inorganic Bleaching agents are indeed preferred. Such inorganic bleaching agents shut down Alkali metal perborate and percarbonate materials. For example For example, sodium perborate (eg, mono- or tetrahydrate) may be used. Suitable inorganic bleaches may also be sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, Include urea peroxyhydrate and sodium peroxide. persulfate (eg OXONE, manufactured by DuPont) may also be used be used. Often are inorganic peroxygen bleach with silicate, borate, sulfate or water-soluble Surfactants coated. Coated percarbonate particles are for example available from various commercial sources, such as FMC, Solway Interox, Tokai Denka and Degussa.

inorganic Peroxygen bleach, e.g. As the perborates, the percarbonates, etc., are preferably combined with bleach activators, which for the in situ production of the peroxyacid, which is the bleach activator corresponds, in aqueous solution (ie during the use of the compositions herein for the washing / bleaching of Substances). Various non-limiting examples for Activators are described in U.S. Patent No. 4,915,854, issued April 10 1990 to Mao et al. And U.S. Patent No. 4,412,934 issued November 1 1983 to Chung et al. Nonanoyloxybenzenesulfonate (NOBS-) and the tetraacetylethylenediamine (TAED) activator are typical and prefers. It can also mixtures thereof are used. See also this already cited U.S. Patent No. 4,634,551 for other typical bleaching agents and Activators useful herein are.

Other useful amido-derived bleach activators are those of the formulas: R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N (R ⁵ ) R ² C (O) L wherein R ^{1 is} an alkyl group of about 6 to about 12 carbon atoms, R ² is an alkylene of 1 to about 6 carbon atoms, R ⁵ is H or alkyl, aryl or alkaryl of from about 1 to about 10 carbon atoms, and L is a suitable leaving group. A leaving group is any group that is displaced from the bleach activator by the perhydrolysis anion due to nucleophilic attack on the bleach activator. A preferred leaving group is phenolsulfonate.

preferred examples for Bleach activators of the above formulas include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate and mixtures thereof, as in the above-cited United States Patent No. 4,634,551.

Another class of useful bleach activators includes the benzoxazine activators described by Hodge et al. in U.S. Patent 4,966,723 issued October 30, 1990. A highly preferred benzoxazine-type activator is:

worin R⁶ H oder eine Alkyl-, Aryl-, Alkoxyaryl- oder Alkarylgruppe mit 1 bis etwa 12 Kohlenstoffatomen ist. Besonders bevorzugte Lactamaktivatoren schließen Benzoylcaprolactam, Octanoylcaprolactam, 3,5,5-Trimethylhexanoylcaprolactam, Nonanoylcaprolactam, Decanoylcaprolactam, Undecenoylcaprolactam, Benzoylvalerolactam, Octanoylvalerolactam, Decanoylvalerolactam, Undecenoylvalerolactam, Nonanoylvalerolactam, 3,5,5-Trimethylhexanoylvalerolactam und Mischungen davon ein. Siehe auch US-Patent Nr. 4,545,784, erteilt an Sanderson, 8. Oktober 1985, das Acylcaprolactame, einschließlich Benzoylcaprolactam, adsorbiert auf Natriumperborat, offenbart.Another class of useful bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams having the formulas:

wherein R ^{6 is} H or an alkyl, aryl, alkoxyaryl or alkaryl group having from 1 to about 12 carbon atoms. Particularly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam, and mixtures thereof. See also U.S. Patent No. 4,545,784, issued to Sanderson, Oct. 8, 1985, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed on sodium perborate.

If Generally, peroxygen bleaches comprise about 2 From% to 30% by weight of the detergent compositions herein. More Preferably, the peroxygen bleach comprises from about 2% by weight to 20% by weight of the compositions. Most preferably, peroxygen bleach is to an extent from about 3% to 15% by weight of the compositions herein. If used, can Bleach activators from about 2% to 10% by weight of the detergent compositions herein. Often Activators are used so that the molar ratio of Bleach to activator in the range of about 1: 1 to 10: 1, more preferably from about 1.5: 1 to 5: 1.

One another highly preferred optional ingredient in the detergent compositions herein is a detergent-active enzyme component. Enzymes can be in the present detergent compositions for a variety of purposes, including the removal of proteinaceous, carbohydrate-containing or triglyceride-containing Stains from substrates, preventing transmission of volatile Dyes washing clothes and the stock refreshment. Suitable enzymes shut down Proteases, amylases, lipases, cellulases, peroxidases, mannanases and mixtures thereof of any suitable origin, such as those of plant, animal, bacterial, fungal and yeast cell origin. The preferred choice is by such factors as the pH activity and / or -Stability, the optimal thermostability and the stability across from active detergents, builders and the like. In this Regard bacterial or fungal enzymes, such as bacterial Amylases and proteases and fungal cellulases, preferred.

"A detergent Enzyme ", as here used means any enzyme that is in a detergent composition for washing clothes a cleansing, stain removing or otherwise beneficial Has effect. Close preferred enzymes for laundry use, without limited to this to be proteases, cellulases, lipases, amylases and peroxidases one.

Enzymes are normally included in detergent compositions in sufficient proportions to provide a "cleaning effective amount." The term "cleaning effective amount" refers to any amount capable of providing a cleansing, stain removing, soil removing, whitening, deodorizing or soaking the freshness-improving effect on substrates such as tissues call. In practical terms, typical amounts for presently commercially available formulations are up to about 5 mg by weight, especially 0.01 mg to 3 mg of active enzyme per gram of the detergent composition. In other words, the compositions typically comprise from 0.001% to 5%, preferably from 0.01% to 1%, by weight of a commercially available enzyme preparation. Protease enzymes are usually present in such commercially available formulations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of the composition. Higher levels of active ingredient may be desired in highly concentrated detergent formulations.

Suitable examples of proteases are the subtilisins obtained from certain strains of B. subtilis and B. licheniformis. One suitable protease with maximum activity throughout the pH range of 8 to 12 is obtained from a strain of Bacillus, called by Novo Industries A / S of Denmark, hereinafter "Novo", developed and sold as ESPERASE ^®. The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include Alcalase ^® and SAVINASE ^® from Novo and MAXATASE ^® from International Bio-Synthetics, Inc., The Netherlands, as well as protease A as in EP 130 756 A , Jan. 9, 1985, and Protease B, as in EP 303 761 A , April 28, 1987, and EP 130 756 A , January 9, 1985, a. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529 A to Novo. Other preferred proteases include those of WO 95/10591 A to Procter & Gamble. If desired, a protease with reduced adsorption and increased hydrolysis, as described in WO 95/07791 to Procter & Gamble, is available. A recombinant trypsin-like protease for detergents useful herein is described in WO 94/25583 to Novo.

Cellulases useful herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 10. U.S. Patent 4,435,307, Barbesgoard et al., March 6, 1984, discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212 producing fungus belonging to the genus Aeromonas, and cellulase derived from the hepatopancreas of a marine mollusk , Dolabella Auricula Solander, is extracted. Suitable cellulases are also disclosed in GB-A-2,075,028; GB-A-2,095,275 and DE-OS 2,247,832. CAREZYME ^® and CELLUZYME® ^® (Novo) are especially useful. See also WO 91/17243 to Novo.

Amylases (α and / or β) may be included to remove carbohydrate-based stains. WO 94/02597, Novo Nordisk A / S, published February 3, 1994, describes cleaning compositions in which amylase mutants are present. See also WO 95/10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known for use in cleaning compositions include α- and β-amylases. Alpha-amylases are well known in the art and include those described in U.S. Patent No. 5,003,257; EP 252,666 ; WO / 91/00353; FR 2,676,456; EP 285,123 ; EP 525,610 ; EP 368,341 and British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are stability-enhanced amylases, described in WO 94/18314, published August 18, 1994, and WO 96/05295, Genencor, published February 22, 1996, and amylase variants with additional modification in the direct parent compound, available from Novo Nordisk A / S, disclosed in WO 95/10603, published in April 95. Amylases useful in EP 277 216 , WO 95/26397 and WO 96/23873 (all by Novo Nordisk). Examples of commercial α-amylases products are Purafect Ox Am ^® from Genencor and Termamyl ^®, Ban ^®, Fungamyl ^® and Duramyl ^®, all available from Novo Nordisk A / S, Denmark. WO 95/26397 describes other suitable amylases: α-amylases, characterized in that they are in a temperature range of 25 ° C to 55 ° C and at a pH in the range of 8 to 10, as measured by the Phadebas ^® α -Amylase activity approach, have a specific activity that is at least 25% higher than the specific activity of Termamyl ^® . Suitable variants of the abovementioned enzymes are those described in WO 96/23873 (Novo Nordisk). Other amylolytic enzymes having improved properties in terms of activity level and the combination of thermal stability and a higher level of activity are described in WO 95/35382.

Suitable lipase enzymes for use in detergents include those formed by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also the lipase in Japanese Patent Application 53,20487, published Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade names Lipase P "Amano" or "Amano-P." , Other suitable commercially available lipases include Amano-CES, Chromobacter viscosum lipases, for example Chromobacter viscosum var. Lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, Chromobacter viscosum lipases from US Biochemical Corp., USA, and Diso ynth Co., The Netherlands, and lipases from Pseudomonas gladioli. Derived from Humicola lanuginosa and commercially available from Novo Enzyme LIPOLASE ^®, see also EP 341,947 , is a preferred lipase for use herein.

preferred Enzyme for the compositions of the present invention is a mannanase enzyme. Included are the following three mannan-cleaving enzymes: EC 3.2.1.25: β-mannosidase, EC 3.2.1.78: endo-1,4-β-mannosidase, hereinafter referred to as "mannanase", and EC 3.2.1.100: 1,4-β-mannobiosidase (IUPAC Classification - Enzyme nomenclature, 1992 ISBN 0-12-227165-3, Academic Press). Preferably, the detergent compositions comprise of the present invention, a β-1,4-mannosidase (E.C. 3.2.1.78), which is called "Mannanase". In fact, it was found that the compositions of the present Invention further comprising a mannanase enzyme excellent Provide color care while she superior Maintain cleaning performance.

Preferably For example, the mannanase enzyme is an alkaline mannanase, as below more preferably, a mannanase derived from a bacterial source descended. Specifically, the compositions of the present invention include Invention an alkaline mannanase selected from the mannanase of the strain Bacillus agaradhaerens NICMB 40482; the mannanase from the Bacillus subtilis strain 168, gene yght; the mannanase from Bacillus sp. I633; the mannanase from Bacillus sp. AAI12 and / or the mannase of the strain Bacillus halodurans. The most preferred mannanase for inclusion in the detergent compositions The present invention is the mannanase enzyme derived from Bacillus sp. I633, as described in WO 99/64619. The term "alkaline Mannanase enzyme "should an enzyme with an enzyme activity of at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity at a given pH in the Range from 7 to 12, preferably 7.5 to 10.5.

• i) ein Polypeptid, produziert von Bacillus agaradhaerens, NCIMB 40482; oder
• ii) ein Polypeptid, umfassend eine Aminosäure-Sequenz, wie in Positionen 32–344 von SEQ-ID NR. 6 dargestellt, wie in WO 99/64619 gezeigt; oder
• iii) ein Analoges des in i) oder ii) definierten Polypeptids, das zu mindestens 70 % mit dem Polypeptid übereinstimmt oder von dem Polypeptid durch Substitution, Reduktion oder Addition einer oder verschiedener Aminosäuren abgeleitet ist oder mit einem polyklonalen Antikörper, der in purifizierter Form gegen das Polypeptid gezüchtet wurde, immunologisch reaktiv ist.

A first more preferred mannanase for use in the present invention is the Bacillus agaradhaerens NICMB 40482 alkaline mannanase described in WO 99/64619. More precisely, this mannanase is:

• i) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or
• ii) a polypeptide comprising an amino acid sequence as described in positions 32-344 of SEQ ID NO. 6 as shown in WO 99/64619; or
• iii) an analog of the polypeptide defined in i) or ii) which is at least 70% identical to the polypeptide or derived from the polypeptide by substitution, reduction or addition of one or more amino acids or with a polyclonal antibody raised in purified form the polypeptide was raised is immunologically reactive.

• (a) Polynucleotidmolekülen, die ein Polypeptid mit Mannanase-Aktivität kodieren und eine Sequenz von Nucleotiden, wie in SEQ-ID Nr. 5 von Nucleotid 94 bis Nucleotid 1032 gezeigt, wie in WO 99/64619 gezeigt;
• (b) Spezieshomologe von (a);
• (c) Polynucleotidmoleküle, die ein Polypeptid mit Mannanase-Aktivität kodieren, das zu mindestens 70 % mit der Aminosäure-Sequenz von SEQ-ID Nr. 6 von Aminosäurerest 32 bis Aminosäurerest 344 identisch ist, wie in WO 99/64619 gezeigt;
• (d) Moleküle, die (a), (b) oder (c) ergänzen; und
• (e) degenerierte Nucleotid-Sequenzen von (a), (b), (c) oder (d).

Also included is the corresponding isolated polypeptide having mannanase activity selected from the group consisting of:

• (a) polynucleotide molecules encoding a polypeptide having mannanase activity and a sequence of nucleotides as shown in SEQ ID NO: 5 from nucleotide 94 to nucleotide 1032 as shown in WO 99/64619;
• (b) species homologue of (a);
• (c) polynucleotide molecules encoding a polypeptide having mannanase activity that is at least 70% identical to the amino acid sequence of SEQ ID NO: 6 from amino acid residue 32 to amino acid residue 344, as shown in WO 99/64619;
• (d) molecules that complement (a), (b) or (c); and
• (e) degenerate nucleotide sequences of (a), (b), (c) or (d).

The Plasmid pSJ1678, which contains the polynucleotide molecule (the DNA sequence) containing the Mannanase encoded, is in a strain of Escherichia coli transformed by the inventors under the Budapest Treaty on the international recognition of the deposit of microorganisms for the Purposes of Patent Procedure in the German Collection of Microorganisms and Cell Cultures GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic of Germany, on May 18, 1998 under the accession number DSM 12180 has been deposited.

• i) kodiert durch den Kodierungsabschnitt der DNA-Sequenz, die in SEQ-ID Nr. 5 dargestellt ist, dargestellt in dem US-Patent Nr. 6,060,299, oder ein Analoges der Sequenz und/oder
• ii) ein Polypeptid, eine Aminosäure-Sequenz umfassend, wie in SEQ-ID NR. 6 dargestellt, die in US-Patent Nr. 6,060,299 dargestellt ist; oder
• iii) ein Analoges des in ii) definierten Polypeptids, das zu mindestens 70 % mit dem Polypeptid übereinstimmt oder von dem Polypeptid durch Substitution, Reduktion oder Addition einer oder verschiedener Aminosäuren abgeleitet ist oder mit einem polyklonalen Antikörper, der in purifizierter Form gegen das Polypeptid gezüchtet wurde, immunologisch reaktiv ist.

A second more preferred enzyme is the mannanase from Bacillus subtilis strain 168 described in U.S. Patent No. 6,060,299. More precisely, this mannanase is:

• i) encoded by the coding portion of the DNA sequence shown in SEQ ID NO: 5 shown in US Patent No. 6,060,299, or an analog of the sequence and / or
• ii) a polypeptide comprising an amino acid sequence as shown in SEQ ID NO. 6, shown in U.S. Patent No. 6,060,299; or
• iii) an analog of the polypeptide as defined in ii) which is at least 70% identical to the polypeptide or derived from the polypeptide by substitution, reduction or addition of one or more of the amino acids, or immunologically reactive with a polyclonal antibody raised in purified form against the polypeptide.

• (a) Polynucleotidmolekülen, die ein Polypeptid mit Mannanase-Aktivität kodieren und eine Sequenz von Nucleotiden umfassen, wie in SEQ-ID NR. 5 dargestellt, wie in US-Patent Nr. 6,060,299 dargestellt
• (b) Spezieshomologe von (a);
• (c) Polynucleotidmoleküle, die ein Polypeptid mit Mannanase-Aktivität kodieren, das zu mindestens 70 % mit der Aminosäure-Sequenz von SEQ-ID Nr. 6, wie in US-Patent Nr. 6,060,299 gezeigt;
• (d) Moleküle, die (a), (b) oder (c) ergänzen; und
• (e) degenerierte Nucleotid-Sequenzen von (a), (b), (c) oder (d).

Also included is the corresponding isolated polypeptide having mannanase activity selected from the group consisting of:

• (a) Polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO. 5 as shown in U.S. Patent No. 6,060,299
• (b) species homologue of (a);
• (c) polynucleotide molecules encoding a polypeptide having mannanase activity that is at least 70% of the amino acid sequence of SEQ ID NO: 6 as shown in US Patent No. 6,060,299;
• (d) molecules that complement (a), (b) or (c); and
• (e) degenerate nucleotide sequences of (a), (b), (c) or (d).

• i) ein Polypeptid, das von Bacillus sp. I633 produziert wird;
• ii) ein Polypeptid, eine Aminosäure-Sequenz umfassend, wie in Positionen 31–330 von SEQ-ID NR. 2 dargestellt, wie in WO 99/64619 gezeigt; oder
• iii) ein Analoges des in i) oder ii) definierten Polypeptids, das zu mindestens 65 % mit dem Polypeptid übereinstimmt oder von dem Polypeptid durch Substitution, Reduktion oder Addition einer oder verschiedener Aminosäuren abgeleitet ist oder mit einem polyklonalen Antikörper, der in purifizierter Form gegen das Polypeptid gezüchtet wurde, immunologisch reaktiv ist.

A third, more preferred mannanase is described in WO 99/64619. More precisely, this mannanase is:

• i) a polypeptide derived from Bacillus sp. I633 is produced;
• ii) a polypeptide comprising an amino acid sequence as set forth in positions 31-330 of SEQ ID NO. 2 as shown in WO 99/64619; or
• iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% identical to the polypeptide or derived from the polypeptide by substitution, reduction or addition of one or more amino acids or with a polyclonal antibody raised in purified form the polypeptide was raised is immunologically reactive.

• (a) Polynucleotidmolekülen, die ein Polypeptid mit Mannanase-Aktivität kodieren und eine Sequenz von Nucleotiden, wie in SEQ-ID Nr. 1 von Nucleotid 94 bis Nucleotid 990 in WO 99/64619 identisch ist;
• (b) Spezieshomologe von (a);
• (c) Polynucleotidmoleküle, die ein Polypeptid mit Mannanase-Aktivität kodieren, das zu mindestens 65 % mit der Aminosäure-Sequenz von SEQ-ID Nr. 2 von Aminosäurerest 31 bis Aminosäurerest 330 in WO 99/64619;
• (d) Moleküle, die (a), (b) oder (c) ergänzen; und
• (e) degenerierte Nucleotid-Sequenzen von (a), (b), (c) oder (d).

Also included is the corresponding isolated polynucleotide molecule selected from the group consisting of:

• (a) polynucleotide molecules encoding a polypeptide having mannanase activity and a sequence of nucleotides as identical in SEQ ID NO: 1 from nucleotide 94 to nucleotide 990 in WO 99/64619;
• (b) species homologue of (a);
• (c) polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% of the amino acid sequence of SEQ ID NO: 2 from amino acid residue 31 to amino acid residue 330 in WO 99/64619;
• (d) molecules that complement (a), (b) or (c); and
• (e) degenerate nucleotide sequences of (a), (b), (c) or (d).

The Plasmid pBXM3 containing the polynucleotide molecule (the DNA sequence), the one Mannanase of the present invention comprises, is in a Strain of Escherichia coli transformed by the inventors according to the Budapest Contract over the international recognition of the deposit of microorganisms for the Purposes of Patent Procedure in the German Collection of Microorganisms and Cell Cultures GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic of Germany, on May 29, 1998 under the accession number DSM 12197 was deposited.

• i) ein Polypeptid, das von Bacillus sp. AAI 12 produziert wird;
• ii) ein Polypeptid, eine Aminosäure-Sequenz umfassend, wie in Positionen 32–362 von SEQ-ID NR. 10 dargestellt, wie in WO 99/64619 gezeigt; oder
• iii) ein Analoges des in i) oder ii) definierten Polypeptids, das zu mindestens 65 % mit dem Polypeptid übereinstimmt oder von dem Polypeptid durch Substitution, Reduktion oder Addition einer oder verschiedener Aminosäuren abgeleitet ist oder mit einem polyklonalen Antikörper, der in gereinigter Form gegen das Polypeptid gezüchtet wurde, immunologisch reaktiv ist.

A fourth, more preferred mannanase is described in WO 99/64619. More precisely, this mannanase is:

• i) a polypeptide derived from Bacillus sp. AAI 12 is produced;
• ii) a polypeptide comprising an amino acid sequence as shown in positions 32-362 of SEQ ID NO. 10 as shown in WO 99/64619; or
• iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% identical to the polypeptide or derived from the polypeptide by substitution, reduction or addition of one or more amino acids or with a polyclonal antibody raised in purified form the polypeptide was raised is immunologically reactive.

• (a) Polynucleotidmolekülen, die ein Polypeptid mit Mannanase-Aktivität kodieren und eine Sequenz von Nucleotiden umfassen, wie in SEQ-ID Nr. 9 von Nucleotid 94 bis Nucleotid 1086 gezeigt, wie in WO 99/64619 gezeigt;
• (b) Spezieshomologe von (a);
• (c) Polynucleotidmoleküle, die ein Polypeptid mit Mannanase-Aktivität kodieren, das zu mindestens 65 % mit der Aminosäure-Sequenz von SEQ-ID Nr. 10 von Aminosäurerest 32 bis Aminosäurerest 362 identisch ist, wie in WO 99/64619 gezeigt;
• (d) Moleküle, die (a), (b) oder (c) ergänzen; und
• (e) degenerierte Nucleotid-Sequenzen von (a), (b), (c) oder (d).

Also included is the corresponding isolated polynucleotide molecule selected from the group consisting of:

• (a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO: 9 from nucleotide 94 to nucleotide 1086 as shown in WO 99/64619;
• (b) species homologue of (a);
• (c) polynucleotide molecules encoding a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ ID NO: 10 from amino acid residue 32 to amino acid residue 362 is as shown in WO 99/64619;
• (d) molecules that complement (a), (b) or (c); and
• (e) degenerate nucleotide sequences of (a), (b), (c) or (d).

The Plasmid pBXM1 containing the polynucleotide molecule (the DNA sequence), the one Mannanase of the present invention comprises, is in a Strain of Escherichia coli transformed by the inventors according to the Budapest Contract over the international recognition of the deposit of microorganisms for the Purposes of Patent Procedure in the German Collection of Microorganisms and Cell Cultures GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic of Germany, on October 7, 1998 under the accession number DSM 12433 was deposited.

• i) ein Polypeptid, das von Bacillus halodurans produziert wird,
• ii) ein Polypeptid, eine Aminosäure-Sequenz umfassend, wie in Positionen 33–331 von SEQ-ID NR. 12 dargestellt, wie in WO 99/64619 gezeigt; oder
• iii) ein Analoges des in i) oder ii) definierten Polypeptids, das zu mindestens 65 % mit dem Polypeptid übereinstimmt oder von dem Polypeptid durch Substitution, Reduktion oder Addition einer oder verschiedener Aminosäuren abgeleitet ist oder mit einem polyklonalen Antikörper, der in purifizierter Form gegen das Polypeptid gezüchtet wurde, immunologisch reaktiv ist.

A fifth, more preferred mannanase is described in WO 99/64619. More precisely, this mannanase is:

• i) a polypeptide produced by Bacillus halodurans,
• ii) a polypeptide comprising an amino acid sequence as set forth in positions 33-331 of SEQ ID NO. 12, as shown in WO 99/64619; or
• iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% identical to the polypeptide or derived from the polypeptide by substitution, reduction or addition of one or more amino acids or with a polyclonal antibody raised in purified form the polypeptide was raised is immunologically reactive.

• a) Polynucleotidmolekülen, die ein Polypeptid mit Mannanase-Aktivität kodieren und eine Sequenz von Nucleotiden umfassen, wie in SEQ-ID Nr. 11 von Nucleotid 97 bis Nucleotid 993 gezeigt, wie in WO 99/64619 gezeigt;
• (b) Spezieshomologe von (a);
• (c) Polynucleotidmoleküle, die ein Polypeptid mit Mannanase-Aktivität kodieren, das zu mindestens 65 % mit der Aminosäure-Sequenz von SEQ-ID Nr. 12 von Aminosäurerest 33 bis Aminosäurerest 331 identisch ist, wie in WO 99/64619 gezeigt;
• d) Moleküle, die (a), (b) oder (c) ergänzen; und
• e) degenerierte Nucleotid-Sequenzen von (a), (b), (c) oder (d).

Also included is the corresponding isolated polynucleotide molecule selected from the group consisting of:

• a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO: 11 from nucleotide 97 to nucleotide 993 as shown in WO 99/64619;
• (b) species homologue of (a);
• (c) polynucleotide molecules encoding a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ ID NO: 12 from amino acid residue 33 to amino acid residue 331, as shown in WO 99/64619;
• d) molecules that complement (a), (b) or (c); and
• e) degenerate nucleotide sequences of (a), (b), (c) or (d).

The Plasmid pBXM5, which comprises the polynucleotide molecule (the DNA sequence), which encodes a mannanase of the present invention is in a Strain of Escherichia coli transformed by the inventors according to the Budapest Contract over the international recognition of the deposit of microorganisms for the Purposes of Patent Procedure in the German Collection of Microorganisms and Cell Cultures GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic of Germany, on October 9, 1998 under the accession number DSM 12441 has been deposited.

The Enzyme-containing compositions herein may optionally also be added to about From 0.001% to about 10% by weight, preferably to about 0.005% by weight. to about 8 wt.%, most preferably u about 0.01 wt.% to about 6 wt .-% contain an enzyme stabilization system. The enzyme stabilization system can be any stabilization system that works with the cleaning effect Enzyme compatible is. Such a system may be inherent to other formulatory agents be provided or added separately, for example by the formulator or a manufacturer of ready-to-use detergent enzymes. Such stabilization systems may include, for example, calcium ions, boric acid, Propylene glycol, short chain carboxylic acids, boronic acids and Mixtures of these include and are designed to be different Stabilization problems depending on the type and physical form of the Detergent composition.

The laundry detergent compositions of the present invention may also include compounds for inhibiting the dye transfer of releasable and suspended dyes that occur during fabric wash operations of colored fabrics from one fabric to another. These are generally present in the laundry detergent compositions of the invention at a level of from 0.001% to 10%, preferably from 0.01% to 2%, more preferably 0.05% by weight. to 1% by weight. Polymeric dye transfer inhibitors are used to inhibit the transfer of dyestuffs from colored fabrics to fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to bind to other articles in the wash. Particularly suitable polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyr rolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.

a) polyamine N-oxide polymers

The polyamine N-oxide polymers suitable for use contain units having the following structural formula:

R sind eine aliphatische, ethoxylierte aliphatische, aromatische, heterocyclische oder alicyclische Gruppe oder irgendeine Kombination davon, an die der Stickstoff der N-O-Gruppe gebunden sein kann, oder die N-O-Gruppe ist ein Teil dieser Gruppen.Where P is a polymerizable moiety to which the RNO group may be attached, or wherein the RNO group is part of the polymerizable moiety, or a combination of both.

R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof to which the nitrogen of the NO group may be attached, or the NO group is a part of these groups.

worin R1, R2 und R3 aliphatische Gruppen, aromatische, heterocyclische oder alicyclische Gruppen oder Kombinationen davon sind, x oder/und y oder/und z 0 oder 1 sind und worin der Stickstoff der N-O-Gruppe angefügt sein kann oder worin der Stickstoff der N-O-Gruppe einen Teil dieser Gruppen bildet.The NO group can be represented by the following general structures:

wherein R1, R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x and / or y and / or z are 0 or 1 and wherein the nitrogen may be added to the NO group or wherein the nitrogen is the NO Group forms part of these groups.

The N-O group may be part of the polymerizable unit (P) or attached to the polymer backbone be, or a combination of both.

suitable Polyamine N-oxides wherein the N-O group forms part of the polymerizable Unit comprise polyamine N-oxides wherein R is aliphatic, aromatic, alicyclic or heterocyclic groups.

A Class of these polyamine N-oxides includes the group of polyamine N-oxides, wherein the nitrogen of the N-O group forms part of the R group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, Acridine and derivatives thereof.

A another class of polyamine N-oxides comprises the group of polyamine N-oxides, wherein the Nitrogen of the N-O group is attached to the R group.

Other suitable polyamine N-oxides are those polyamine oxides in which the NO group to the polymerizable unit is added.

The preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen is functional N-O group is part of the R group.

Examples of these classes are polyamine oxides wherein R is a heterocyclic Compound is such as pyridine, pyrrole, imidazole and derivatives thereof.

A Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R is aromatic, heterocyclic or alicyclic groups, wherein the nitrogen is functional N-O group is attached to these R groups.

Examples of these classes are polyamine oxides in which the R groups are aromatic could be, like phenyl.

each Polymer backbone may be used as long as the amine oxide polymer formed is water-soluble and color transfer inhibiting Features. Examples of suitable polymer backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, Polyacrylates and mixtures thereof.

The Amine N-oxide polymers of the present invention are usually a relationship from amine to amine N-oxide from 10: 1 to 1: 1,000,000. The amount of amine oxide groups, which are present in the polyamine oxide polymer, however, can be replaced by suitable Copolymerization or by a suitable degree of N-Oxi dation be varied. Preferably, the ratio of amine to amine N-oxide is from 2: 3 to 1: 1,000,000. More preferably from 1: 4 to 1: 1 000 000, most preferred from 1: 7 to 1: 1 million. The polymers of the present invention include indeed random or block copolymers where a monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or Not. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably a pKa <7, more preferably a pKa <6.

The Polyamine oxides can be achieved in almost every degree of polymerization. The degree of polymerization is not critical, provided that the material has the desired water solubility and ability for dye suspensibility having.

Usually the average molecular weight is in the range of 500 up to 1,000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The N-vinylimidazole-N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range of 5,000-1,000,000, preferably from 5,000 to 200,000.

strongly preferred polymers for use in the laundry detergent compositions of the present invention include a polymer consisting of N-vinylimidazole-N-vinylpyrrolidone copolymers is selected, wherein the polymer has an average molecular weight range from 5,000 to 50,000, more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.

Of the average molecular weight range was determined by light scattering, as in Barth, H.G. and Mays, J.W., Chemical Analysis, Vol. 113, "Modern Methods of Polymer Characterization ".

strongly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have a average molecular weight range of 5,000 to 50,000; more preferably from 8,000 to 30,000; most preferably from 10,000 up to 20,000.

The N-vinylimidazoles-N-vinylpyrrolidone copolymers characterized thereby are that they have this average molecular weight range have excellent dye transfer inhibiting properties, while the cleaning performance of detergent compositions formulated therewith not adversely affect.

The N-vinylimidazole-N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazoles to N-vinylpyrrolidone of 1 to 0.2, more preferred from 0.8 to 0.3, most preferably from 0.6 to 0.4.

c) polyvinylpyrrolidone

The Laundry detergent compositions of the present invention also polyvinylpyrrolidone ("PVP") with an average Molecular weight of about 2,500 to about 400,000, preferably from from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000 and most preferably from about 5,000 to about 15,000. Suitable polyvinylpyrrolidones are available from ISP Corporation, New York, NY, USA and Montreal, Canada, under the trade names PVP K-15 (Viscosity Molecular Weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000) and PVP K-90 (average Molecular weight 360,000) are commercially available. Other suitable polyvinylpyrrolidones, commercially available from BASF Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones, the experts in the field of detergents are known (see for example EP-A-262,897 and EP-A-256,696).

d) Polyvinyloxazolidone:

The Laundry detergent compositions of the present invention also polyvinyloxazolidone as a polymeric dye transfer inhibitor use. The Polyvinyloxazolidone have an average Molecular weight of about 2,500 to about 400,000, preferably about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000 and most preferably from about 5,000 to about 15,000.

e) polyvinylimidazole:

The Laundry detergent compositions of the present invention also use polyvinylimidazole as a polymeric dye transfer inhibitor. The polyvinylimidazoles have an average of about 2,500 until about 400,000, preferably about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000 and most preferably from about 5,000 to about 15,000.

f) Crosslinked polymers:

Crosslinked polymers are polymers whose skeletons are interconnected to some degree; these compounds may be chemical or physical in nature, possibly with active groups in the backbone or branching; Crosslinked polymers are described in Journal of Polymer Science, Vol. 22, pp. 1035-1039. In one embodiment, the crosslinked polymers are constructed to form a three-dimensional rigid structure that can include dyes in the pores formed by the three-dimensional structure. In another embodiment, the crosslinked polymers include the dyes by swelling. Such crosslinked polymers are in US 5,912,221 described.

Further, the laundry detergent composition of the present invention may optionally comprise a pearlescing agent to improve the aesthetic appearance of the product. Suitable pearlescing agents are those well known in the art to provide pearlescent effects in surfactant compositions. For example, pearlescent mica pigments such as Iriodin from Merck or an equivalent, z. Mearlin Magnapearl from Meare Corp., or organic compounds having the property of crystallizing as pearlescent needles in the product. Typical compounds with this property are polyol esters such as ethylene glycol mono- (EGMS) or distearate (EGDS) or polyethylene glycol mono- (PGMS) or distearate (PGDS). There are several trade sources for these materials. For example, but not limited to, PEG6000MS from Stepan, Empilan EGDS / A from Albright & Wilson are all suitable pearlescing agents. Other suitable pearlescing agents are found in WO 99/09944. "It is well known in the art to further add a pearlescent crystallization improver to liquid products containing pearlescing agents Suitable enhancers are the acids, salts, alcohols and esters having a hydrophobic moiety at least 16C, preferably at least 18C, as in EP 520 551 B described. It has surprisingly been found that the semipolar nonionic surfactants of the present invention, and preferably the amine oxide compounds, can function as a crystallization improver for organic pearlescing agents. Liquid detergent compositions containing an organic pearlescing agent and a semi-polar nonionic Surfactant, preferably an amine oxide, exhibit a very attractive pearlescent appearance. It has also been found that liquid laundry detergent compositions comprising the surfactant system of the present invention exhibit a particularly attractive pearlescent effect.

Preparation of the detergent composition

The Laundry detergent compositions according to the invention can by combining the basic and optional components in the required concentrations in any suitable Order and produced by any conventional means become.

Granular compositions are prepared, for example, by adding granular components, z. Surfactants, builders, water, etc., as a slurry and the resulting slurry spray-dried to a low level of residual moisture (5-12%). The remaining dry ingredients, eg. B. granules the basic cycloamine-based textile treatment materials, can in granular Powder form with the spray-dried granule be mixed in a rotating mixing drum. The liquid components, z. B. Solutions the basic cycloamine-based textile treatment materials, Enzymes, binders and fragrances can affect the resulting Granules sprayed on to form the final detergent composition.

Liquid detergent compositions can be made by their basic and optional Ingredients in each one you want Sequence together to provide compositions which contain the components in the required concentrations. Inventive liquid compositions can also in "compact Form ", in these cases contain the liquid detergent compositions according to the invention a smaller amount of water compared to conventional liquid detergents. encore the cycloamine-based polymer, oligomer or copolymer materials to liquid Detergent or other aqueous Compositions of this invention can be prepared by simple mixing the desired Cycloamine-based fabric treatment materials in the liquid solutions achieved become.

Fabric washing process

The The present invention also provides a method of washing Fabrics in a way prepared by which through the combination of the semi-polar nonionic surfactant and those used herein Cycloamine-based polymer, oligomer or copolymer materials Benefits in terms of textile cleaning and textile appearance. In such a process, these substances become me an aqueous wash solution which is selected from an effective amount of the above or detergent compositions described is formed the individual components of these compositions is formed. The contact of the substances with washing solution is generally under Movement conditions provided, although the compositions of the present invention also for not agitated watery soaking for the fabric cleaning and treatment can be used. As explained above, is it prefers that the washing solution a pH of less than about 10.0, preferably has a pH of less than 9.5 and most preferably has a pH of less than 7.5.

The Movement is preferably carried out in a washing machine to to achieve a good cleaning. Washing preferably follows drying the wet cloth in a conventional clothes dryer. An effective Amount of high-density liquid or more granular Detergent composition in the aqueous washing solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.

Examples

The explain the following examples the compositions and methods of the present invention, However, should not necessarily limit the scope of the invention or otherwise define.

Examples 1-15 illustrate the synthesis of the cycloamine-based polymer.

example 1

Synthesis of the adduct Imidazole and epichlorohydrin (ratio imidazole: epichlorohydrin 1: 1):

The polycationic condensate is made by reacting imidazole and epichlorohydrin produced. In a round bottom flask equipped with a magnetic stirrer, a cooler and a thermometer are imidazole (0.68 mol) and 95 ml of water. The solution gets to 50 ° C heated followed by the dropwise addition of epichlorohydrin (0.68 mol). After all Epichlorohydrin is added, the temperature is raised to 80 ° C, until all Alkylating agent is consumed. The generated condensate points a molecular weight of about 12,500.

Example 2

Synthesis of the adduct Imidazole and epichlorohydrin (ratio Imidazole: epichlorohydrin 1.4: 1)

In a round bottom flask equipped with a magnetic stirrer, a condenser and a equipped with a thermometer are imidazole (0.68 mol) and Added 95 ml of water. The solution gets to 50 ° C heated followed by the dropwise addition of epichlorohydrin (0.50 mole). After all Epichlorohydrin is added, the temperature is raised to 80 ° C, until all Alkylating agent is consumed. The generated condensate points a molecular weight of about 2,000.

Example 3

Synthesis of the adduct Piperazine, morpholine and epichlorohydrin (ratio 1.8 / 0.8 / 2.0)

In a round bottom flask equipped with a stirrer, a thermometer, a Dropping funnel and a reflux condenser equipped 154.8 g (1.8 mol) of piperazine and 69.6 g (0.8 mol) of morpholine and weighed 220 ml of water. After receiving a clear solution at 40 ° C became, became the solution heated to 55-65 ° C and with vigorous stirring were 185 g (2 moles) of epichlorohydrin at such a rate admitted that the temperature did not exceed 80 ° C. After all Epichlorohydrin was added, the reaction mixture at 85 ° C heated until all Alkylating agents were consumed (negative Preussmann test after 4 hours). 108.8 g (0.68 mol) of 25% NaOH and 40 g of water were added and the reaction mixture was for a further Hour at 85 ° C touched. Then another 47 g of water was added and the mixture was allowed to cool to room temperature.

Example 4

Synthesis of the adduct Piperazine and epichlorohydrin (ratio imidazole: epichlorohydrin 1: 1):

In a round bottom flask equipped with a magnetic stirrer, a condenser and a equipped with a thermometer, piperazine (0.68 mol) and 95 ml of water. The solution gets to 50 ° C heated followed by the dropwise addition of epichlorohydrin (0.68 mol). After all Epichlorohydrin is added, the temperature is raised to 80 ° C, until all Alkylating agent is consumed.

Example 5

To the Condensate in Example 4 becomes a 1.4 mole equivalent of methyl chloride Piperazine-based and mixed until all the methyl chloride is consumed.

Example 6

Synthesis of the adduct Imidazole, piperazine and epichlorohydrin (ratio of imidazole: piperazine: epichlorohydrin = 1: 3: 4)

68.8 g (1.0 mol) of imidazole and 260.6 g (3.0 mol) of piperazine were dissolved in 700.2 g g of water dissolved and at a temperature of 50-60 ° C Added 370 g (4.0 mol) of epichlorohydrin dropwise. After the addition was completed, the reaction mixture was another 5 hours at 80 ° C touched.

Example 7

(a) Reaction of bis (aminopropyl) piperazine with epichlorohydrin in a molar ratio of 2: 1

600 g (3 mol) of bis (aminopropyl) piperazine was dissolved in 750 g of water. These solution was at 90 ° C heated. Once this temperature was reached, 140.1 g (1.5 mol) of epichlorohydrin within 60 minutes at 90 ° C added. The reaction mixture was then stirred at 90 ° C for 150 minutes. After that no epichlorohydrin could be detected. The condensation product contained NH groups.

(b) permethylation of the under (a) recovered condensation product

99.7 g (content of NH groups was 0.87 mol) of that obtained according to (a) Condensation product was treated with 100.3 g (2.18 mol) of formic acid (99 %) while stirring and cooling mixed in an ice bath. 104.5 g (1.045 mol) of formaldehyde in the Form of an aqueous solution with a strength of 30% by weight over 20 minutes at room temperature added. The reaction mixture was then warmed gently to 60 ° C. at about 50 ° C The development of carbon dioxide started from the reaction mixture and became at 60 ° C strong, so that the heating could be removed. After the development of carbon dioxide had slowed down, the reaction mixture became Refluxed for 12 hours. After cooling, 100 ml were concentrated hydrochloric acid added and the water was removed from the reaction mixture. 153.6 g of solids were recovered and dissolved in water, giving a solution with a strength 50% by weight of a cycloamine-based polymer was formed, which are essentially free of primary and secondary amino groups is. As determined by 13C NMR spectroscopy, more than 90 % of NH groups in tertiary nitrogen atoms transformed. The amount of quaternary Ammonium groups in the polymer was below 5%. The aqueous polymer solution had a pH of 9.58. The k value of the polymer was 8.6.

Example 8

A solution from 92.6 g (1.36 mol) of imidazole in 140.5 g of water was heated to 50 ° C and in the course of 10 minutes with an aqueous solution of 8.2 g (0.07 mol) of sodium salt of 2-chloroacetic acid combined in 50 g of water. The solution will then be at 65 ° C heated until the entire sodium salt of 2-chloroacetic acid is reacted, as analytically can be determined by the chloride ion content of the solution. 5.6 g (0.07 mol) of an aqueous solution from sodium hydroxide with a starch of 50% by weight was added and 89.7 g (0.97 mol) of epichlorohydrin were added with stirring within 30 minutes added so that the temperature of the reaction mixture is in the range of 55 to 65 ° C held could be. After the addition of epichlorohydrin, the reaction mixture became at 80 ° C heated and stirred for 4 hours at this temperature. After this period could no alkylating agent can be detected. 377.7 g one yellowish aqueous solution an amphoteric amine-based polymer having a net cationic charge of 4.2 mequiv / g of polymer were obtained. The solution had a pH of 6.97 and contained 50.3% water, 0.06% glycolic acid and less than 0.05% 2-chloro acetic acid. The molecular weight of the polymer was Mn = 700, Mw = 1,460 and Mw / Mn = 2.1.

Example 9

According to the in Example 8, 92.6 g (1.36 mol) of imidazole, 16.3 g (0.14 mol) of the sodium salt of 2-chloroacetic acid, 11.2 g (0.14 mol) of an aqueous solution of sodium hydroxide in one starch of 50% by weight and 86.1 g (0.93 mol) of epichlorohydrin. 386.3 g of a yellowish aqueous solution an amphoteric amine-based polymer having a net cationic charge of 3.4 mequiv / g of polymer was obtained. The solution had a pH of 7.10 and contained 49.6% water, 0.1% glycolic acid and less than 0.05% 2-chloro acetic acid. The molecular weight of the polymer was Mn = 650, Mw = 1,320 and Mw / Mn = 2.0.

Example 10

According to the in Example 8, 92.6 g (1.36 mol) of imidazole, solved in 122.6 g of water, 39.6 g (0.34 mol) of the sodium salt of 2-chloroacetic acid dissolved in 100 g of water, 27.2 g (0.34 mol) of an aqueous solution of sodium hydroxide in a strength reacted 50 wt .-% and 76.8 g (0.83 mol) of epichlorohydrin. 386.3 g of a yellowish aqueous solution an amphoteric amine-based polymer having a net cationic charge of 2.8 mequiv / g was obtained. The solution had a pH of 7.82 and contained 53.4% water, 0.2% glycolic acid and less than 0.05% 2-chloro acetic acid. The molecular weight of the polymer was Mn = 540, Mw = 1,060 and Mw / Mn = 2.0.

Example 11

example 7 was repeated with the exceptions that 68.1 g (1.0 mol) of imidazole, solved in 54.9 g of water, 72.0 g (0.6 mol) of the sodium salt of 2-chloroacetic acid dissolved in 150 g of water, 48.0 g (0.6 mol) of an aqueous solution of sodium hydroxide in a strength of 50 wt .-% and 64.8 g (0, / mol) of epichlorohydrin reacted. 446.4 g of a dark yellow aqueous solution an amphoteric amine-based polymer having a net cationic charge of 3.2 mequiv / g were obtained. The solution had a pH of 12.29 and contained 48.2% water, 0.5% glycolic acid and less than 0.05% 2-chloro acetic acid. The Molecular weight of the polymer was Mn = 740, Mw = 1.690 and Mw / Mn = 2,3.

Example 12

example 8 was repeated with the exceptions that 71.5 g (1.05 mol) of imidazole, solved in 116.3 g of water, 40.8 g (0.34 mol) of the sodium salt of 2-chloroacetic acid, dissolved in 100 g of water, 27.2 g (0.24 mol) of an aqueous solution of sodium hydroxide in a strength reacted 50 wt .-% and 76.8 g (0.83 mol) of epichlorohydrin. 427.6 g of a yellow aqueous solution an amphoteric amine-based polymer having a net cationic charge of 3.7 mequiv / g and a K value of 9.5 were obtained. The solution had a pH of 11.62 and contained 54.2% water, 0.3% glycolic acid and less than 0.05% 2-chloroacetic acid. The Molecular weight of the polymer was Mn = 1,050, Mw = 2,380 and Mw / Mn = 2,3.

Example 13

68.1 g (1 mol) of imidazole were dissolved in 73.6 g of water and allowed to reach a temperature from 50 ° C heated. As soon as reached this temperature, a solution of 73.5 g (0.34 mol) was added. of the sodium salt of 3-chloro-2-hydroxypropanesulfonic acid in 150 g of water and 27.2 g (0.34 mol) of an aqueous solution of sodium hydroxide a strength of 50% by weight were added simultaneously with stirring over a period of 25 minutes added. The reaction mixture was then at a temperature from 65 to 90 ° C touched, until the entire sodium salt of 3-chloro-2-hydroxypropanesulfonic acid reacts had as analytically by measuring the concentration of chloride ions in the solution was determined. The solution was at 55 ° C cooled and 76.8 g (0.83 mol) of epichlorohydrin became within 30 minutes fed at such a rate that the temperature of the reaction mixture kept at 55 ° C. could be. Upon completion of epichlorohydrin addition, the Reaction mixture at 80 ° C. heated and stirred for 4 hours at this temperature. After this period could no alkylating agent can be determined in the reaction mixture. 461.3 g of a clear yellow aqueous solution an amphoteric amine-based polymer having a net cationic charge of 2.9 mequiv / g and a K value of 10.0 were obtained. The solution had a pH of 11.55 and contained 52.4% water. The molecular weight of the polymer was Mn = 1,800, Mw = 3,490 and Mw / Mn = 1.95.

Example 14

example 13 was repeated except that 34.1 g (0.5 mol) of imidazole, solved in 31.3 g of water, 64.8 g (0.35 mol) of the sodium salt of 3-chloro-2-hydroxypropanesulfonic acid, dissolved in 100 g of water, 24.0 g (0.3 mol) of an aqueous solution of sodium hydroxide in a strength of 50 wt .-% and 32.4 g (0.35 mol) of epichlorohydrin were reacted. 284.1 g of a clear yellow aqueous solution an amphoteric amine-based polymer having a net cationic charge of 3.3 mequiv / g polymer and a K value of 7.6 were obtained. The solution had a pH of 11.92 and contained 51.7% water. The molecular weight of Polymer was Mn = 1,100, Mw = 1,990 and Mw / Mn = 1.80.

EXAMPLE 15

Synthesis of the adduct of Imidazole / piperazine / epi in a ratio of 1.0 / 3.0 / 4.0

• 100% oxidized

68.8 g (1.0 mol) of imidazole and 260.6 g (3.0 mol) of piperazine were dissolved in 700.2 g of water and at a temperature of 50-60 ° C, 370 g (4.0 mol) Epichlorohydrin added dropwise. After the addition was complete, the reaction mixture was stirred at 80 ° C for a further 5 hours. To 237 g of this product (equivalent to 1022 moles of oxidizable nitrogen atoms) was added 80.7 g (1.12 moles) of a 47.2% solution of H2O2 in water over a period of 5 hours at 40 ° C. Thereafter, the mixture was heated to 50-60 ° C until the theoretical amount of H2O2 was consumed. Not transposed H ₂ O ₂ was destroyed by Pt / C and the solution was filtered.

The reaction product was characterized as follows: Water content: 58.6% pH: 2.86 Chloride content: 3.694 mmol / g Mn (GPC): 340 Mw (GPC): 940 Mn / Mw: 2, 8 +/- 0.1

Example 16

The following 2 sets of liquid laundry detergent compositions were prepared according to the invention:

• 1) Das Polymer auf Cycloaminbasis ist ausgewählt aus einer oder mehreren Verbindung(en), die in der unten stehenden Tabelle illustriert sind
• 2) Der Komplexbildner ist ausgewählt von Ethylendiamin-N,N'-dibernsteinsäure, (S,S)-Isomer in der Form seines Natriumsalzes und/oder Diethylentriamin-pentaessigsäure.
• 3) Die Enzyme sind ausgewählt von den herkömmlichen Protease-, Amylase-, Lipase- und/oder Cellulaseenzymen, wie oben stehend beschrieben. Mannanase ist das Mannanaseenzym, das von Novo Nordisk A/S unter der Handelsbezeichnung Mannaway vertrieben wird.
• 4) Das Dispergierpolymer ist ein ethoxyliertes Poly(ethylenimin)polymer mit einem Molekulargewicht zwischen 200 und 3000 und einem EO zwischen 7 und 30

Wherein the components are defined as below:

• 1) The cycloamine-based polymer is selected from one or more compound (s) illustrated in the table below
• 2) The complexing agent is selected from ethylenediamine-N, N'-disuccinic acid, (S, S) -isomer in the form of its sodium salt and / or diethylenetriamine-pentaacetic acid.
• 3) The enzymes are selected from the conventional protease, amylase, lipase and / or cellulase enzymes as described above. Mannanase is the mannanase enzyme marketed by Novo Nordisk A / S under the trade name Mannaway.
• 4) The dispersing polymer is an ethoxylated poly (ethyleneimine) polymer having a molecular weight between 200 and 3000 and an EO between 7 and 30

EXAMPLE 17

The following granular detergent compositions were prepared according to the invention:

Wherein the cellulosic polymer is a carboxymethyl cellulose characterized by

Wherein the cycloamine-based polymer / oligomer is selected from one or more the links below. The chemical structures that shown in the examples below are idealized Structures. Side reactions to be expected during condensation is not shown.

Claims (14)

A laundry detergent composition comprising a semi-polar nonionic surfactant; an amine-based cyclic polymer, oligomer or copolymer of the general formula:

wherein: each T is independently selected from the group consisting of H, C ₁ -C ₁₂ alkyl, substituted alkyl, C ₇ -C ₁₂ alkylaryl,

Wherein W comprises at least one cyclic constituent selected from the group consisting of:

in addition to the at least one cyclic constituent W, also an aliphatic or substituted aliphatic moiety of the general structure

Each B is independently C ₁ -C ₁₂ alkylene, substituted C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ alkenylene, C ₈ -C ₁₂ dialkylarylene, C ₈ -C ₁₂ dialkylarylenediyl and (R ₅ O) _{n is} R ₅ ; Each D is independently C ₂ -C ₆ alkylene; Each Q is independently selected from the group consisting of hydroxy, C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₈ hydroxyalkoxy, amino, C ₁ -C ₁₈ alkylamino, -dialkylamino, -trialkylamino, heterocyclic Monoamino groups and diamino groups; Each R _{1 is} independently selected from the group consisting of H, C ₁ -C ₈ alkyl and C ₁ -C ₈ hydroxyalkyl; Each R _{2 is} independently selected from the group consisting of C ₁ -C ₁₂ -alkylene, C ₁ -C ₁₂ -alkenylene, -CH ₂ -CH (OR ₁ ) -CH ₂ , C ₈ -C ₁₂ -alkarylene, C ₄ -C ₁₂ -dihydroxyalkylene, poly- (C ₂ -C ₄ -alkyleneoxy) -alkylene, H ₂ CH (OH) CH ₂ OR ₂ OCH ₂ CH (OH) CH ₂ and C ₃ -C ₁₂ hydrocarbon units; with the proviso that when R _{2 is} a C ₃ -C ₁₂ hydrocarbon moiety, the hydrocarbon moiety may comprise from 2 to about 4 branching units of the following general structure:

Each R _{3 is} independently selected from the group consisting of H, R ₂ , O, C ₁ -C ₂₀ -hydroxyalkyl, C ₁ -C ₂₀ -alkyl, substituted alkyl, C ₆ -C ₁₁ -aryl, substituted aryl, C ₇ -C ₁₁ -alkylaryl, C ₁ -C ₂₀ -aminoalkyl,

Each R _{4 is} independently selected from the group consisting of H, C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ hydroxyalkyl, aryl and C ₇ -C ₂₂ alkylaryl; Each R _{5 is} independently selected from the group consisting of C ₂ -C ₈ alkylene, C ₂ -C ₈ alkyl substituted alkylene; and A is a compatible monovalent or divalent or polyvalent anion; M is a compatible cation; b = number is required to balance the charge; each x ranges independently from 3 to 1000; each c is independently 0 or 1; each h is independently 1 to 8; each q ranges independently from 0 to 6; each n ranges independently from 1 to 20; each r is independently 0 to 20 and each t is independently 0 to 1, and a conventional laundry detergent component selected from a builder compound and one or more detergent components selected from bleaches, additional enzymes, suds suppressors, dispersants, lime soap dispersants, Soil suspension and anti-redeposition agents and corrosion inhibitors; wherein the composition does not comprise anionic surfactants. Laundry detergent composition according to claim 1, wherein the cyclic polymer, oligomer or copolymer amine-based adducts of two or more compositions, selected from the group consisting of piperazine, piperidine, epichlorohydrin, Epichlorohydrinbenzyl quat, epichlorohydrin methyl quat, morpholine and Mixtures thereof. A laundry detergent composition according to claims 1-2, wherein in the definition of T, each R ₁ , if present, is H and at least one W is selected from the group consisting of:

A laundry detergent composition according to claims 1-3, wherein, in the definition of T, each R ₁ , if present, is H and at least one W is selected from the group consisting of:

The laundry detergent composition of claims 1-4, wherein in the definition of T, each R ₁ , if present, is H and at least one W is selected from the group consisting of:

Laundry detergent composition according to any one of the preceding claims, wherein x is from 3 to 25, preferably from 4 to 20 is. Laundry detergent composition according to any one of the preceding claims, wherein the cyclic polymer, Oligomer or amine-based copolymer in a concentration of 0.01 wt .-% to 5 wt .-%, preferably in a concentration of From 0.1% to 4% by weight, more preferably from 0.75% to 3% by weight the total composition is included. Laundry detergent composition according to any one of the preceding claims, wherein the semi-polar nonionic Surfactant in a concentration of 0.1 wt .-% to 20 wt .-%, preferably from 1 wt% to 10 wt%, more preferably from 2 wt% to 7 wt% the total composition is included. A laundry detergent composition according to any one of the preceding claims wherein the semi-polar nonionic surfactant is an amine oxide surfactant, preferably selected from C ₁₀ -C ₁₈ alkyl dimethyl amine oxide and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxide, C _12-14 alkyl dimethyl amine oxide and / or mixtures thereof, where more preferably that is C _12-14 alkyldimethylamine oxide. Laundry detergent composition according to any one of the preceding claims, further comprising a nonionic Surfactant in a concentration of 1 wt .-% to 50 wt .-%, preferably from 5 % By weight to 30% by weight, more preferably from 15% by weight to 25% by weight the total composition. Laundry detergent composition according to any of the preceding claims, further comprising an ingredient includes, selected of a cellulose-based polymer or oligomer, a cationic one Surfactant, a dye transfer inhibiting polymer, a mannanase enzyme, a pearlescing agent and / or Mixtures thereof. Laundry detergent composition according to claim 11, wherein the pearlescent agent is selected from the group consisting of ethylene glycol distearate, ethylene glycol monostearate and / or mixtures thereof. Use of a laundry detergent composition according to claims 1-12, to provide cleaning and fabric care properties. Use of a laundry detergent composition according to claims 1-12, to provide textile conservation.