DE69923855T2 - DETERGENT COMPOSITIONS CONTAINED A COMBINATION OF CYCLIC AMINE BASED COPOLYMERS AND HYDROPHOBIC MODIFIED CELLULOSES - Google Patents

Description

TECHNICAL TERRITORY

The The present invention relates to compositions, either in liquid or granular Mold, for use in laundry applications, wherein the compositions comprise certain polymeric, oligomeric or copolymeric Cycloamine-based materials in combination with hydrophobically modified Carboxymethylcellulose include. This combination gives fabrics and textiles used in washing solutions be washed, which are formed from these compositions, Benefits in terms of appearance and integrity or tear resistance.

BACKGROUND THE INVENTION

It is natural Known to be the alternating cycles of using and washing of fabrics and textiles, such as worn garments and Clothing, the appearance and tear strength of the fabric and Textile items, which are so used and washed, inevitably impaired. 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. However, you can the washing itself, over many cycles, the deterioration of tear resistance and appearance reinforce and contribute to such substances and textiles.

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 Fluff, lint, or "pills" that build up the surface of substances are visible and the as new appearance of the substance reduce. Furthermore can be repeated washing of fabrics and textiles, especially with bleach-containing washing products, the color of fabrics and textiles remove and as a result decreased 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, there is clearly a continuing need to To find materials, the laundry detergent products could be added and dealing with the fibers of fabrics and textiles by means of of these laundry detergent products be washed, connect and thereby the tendency of the washed Minimize fabrics and textiles to worsen their appearance. Each of these additional materials for Detergent products should be natural to be able to favor the look and tear resistance of the fabric affect without the ability the laundry detergent, to exercise its cloth cleaning function, unduly impair it. The present invention is directed to the use of a mixture from certain polymeric, oligomeric or copolymeric materials cycloamine-based and hydrophobically-modified cellulose in laundry applications directed, which behave in this desired way.

SUMMARY THE INVENTION

• a) von 1 Gew.-% bis 80 Gew.-% Tenside, ausgewählt aus der Gruppe, bestehend aus nichtionischen, anionischen, kationischen, amphoteren, zwitterionischen Tensiden und Mischungen davon; und
• b) mindestens 0,01 Gew.-%, vorzugsweise mindestens 0,1 Gew.-%, am meisten bevorzugt mindestens 0,5 Gew.-% und unter 50 Gew.-%, vorzugsweise unter 25,0 Gew.-%, am meisten bevorzugt unter 5,0 Gew.-%, eine Mischung aus Polymeren, Oligomeren oder Copolymeren auf Cycloaminbasis und Polymeren oder Oligomeren auf der Basis hydrophob modifizierter Cellulose, worin das Verhältnis der hydrophob modifizierten Cellulose zu dem Polymer, Oligomer oder Copolymer auf Cycloaminbasis im Bereich von 1000 :1 bis 1: 1000 liegt.

The present invention is directed to a detergent composition comprising:

• a) from 1% to 80% by weight of surfactants selected from the group consisting of nonionic, anionic, cationic, amphoteric, zwitterionic surfactants and mixtures thereof; and
• b) at least 0.01% by weight, preferably at least 0.1% by weight, most preferably at least 0.5% by weight and less than 50% by weight, preferably less than 25.0% by weight, most preferably below 5.0% by weight, a mixture of polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobically modified cellulose, wherein the ratio of the hydrophobically modified cellulose to the polymer, oligomer or copolymer based on cycloamine in Range from 1000: 1 to 1: 1000.

worin
jedes T unabhängig ausgewählt ist aus der Gruppe, bestehend aus H, C₁-C₁₂-Alkyl, substituiertem Alkyl,
C₇-C₁₂-Alkylaryl,
-(CH₂)_hCOOM, -(CH₂)_hSO₃M, CH₂CH(OH)SO₃M, -(CH₂)_hOSO₃M,

• – worin W mindestens einen cyclischen Bestandteil umfasst, der ausgewählt ist aus der Gruppe bestehend aus:
  
  zusätzlich zu dem mindestens einen cyclischen Bestandteil kann W auch eine aliphatische oder substituierte aliphatische Einheit der 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-, Trialkylamino-Gruppen, 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-Hydrocarbyleinheiten; mit der Maßgabe, dass, wenn R₂ eine C₃-C₁₂-Hydrocarbyleinheit ist, die Hydrocarbyleinheit 2 bis 4 Verzweigungseinheiten der allgemeinen Struktur
  
  umfassen kann, worin jedes R₃ unabhängig ausgewählt ist aus der Gruppe, bestehend aus H, O, R₂, C₁-C₂₀
• – Hydroxyalkyl, C₁-C₂₀-Alkyl, substituiertem Alkyl, C₆-C₁₁-Aryl, substituiertem Aryl, C₇-C₁₁
• – Alkylaryl, C₁-C₂₀-Aminoalkyl,
• – (CH₂)_hCOOM, -(CH₂)_hSO₃M, CH₂CH(OH)SO₃M, -(CH₂)_hOSO₃M,
  
• – jedes R₄ unabhängig ausgewählt ist aus der Gruppe, bestehend aus H, C₁-C₂₂-Alkyl, C₁-C₂₂-Hydroxyalkyl, Aryl und C₇-C₂₂-Alkylaryl;
• – jedes R₅ unabhängig ausgewählt ist aus der Gruppe, bestehend aus C₂-C₈-Alkylen, alkylsubstituiertem C₂-C₈
• – Alkylen; und A ein verträgliches einwertiges oder mehrwertiges Anion ist; M ein veträgliches Kation ist; b = Zahl, die erforderlich ist, um die Ladung auszugleichen; jedes x unabhängig von 3 bis 1000 ist; jedes c unabhängig 0 oder 1 ist; jedes h unabhängig 1 bis 8 ist; jedes q unabhängig von 0 bis 6 ist; jedes n unabhängig von 1 bis 20 ist; jedes r unabhängig von 0 bis 20 ist und jedes t unabhängig von 0 bis 1 ist.

The cycloamine-based polymer, oligomer or polymer materials suitable for use in laundering processes and providing the desired appearance and tear resistance benefits of fabrics can be 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,
- (CH ₂ ) _h COOM, - (CH ₂ ) _h SO ₃ M, CH ₂ CH (OH) SO ₃ M, - (CH ₂ ) _h OSO ₃ M,

• 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 be an aliphatic or substituted aliphatic moiety of the general structure
  
  include; 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, Groups, heterocyclic monoamino groups and diamino groups;
• Each R1 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 hydrocarbyl moieties; with the proviso that when R _{2 is} a C ₃ -C ₁₂ hydrocarbyl moiety, the hydrocarbyl moiety is 2 to 4 branch units of the general structure
  
  wherein each R _{3 is} independently selected from the group consisting of H, O, R ₂ , 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,
• - (CH ₂ ) _h COOM, - (CH ₂ ) _h SO ₃ M, CH ₂ CH (OH) SO ₃ M, - (CH ₂ ) _h OSO ₃ M,
  
• 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, alkyl substituted C ₂ -C ₈
• - alkylene; and A is a compatible monovalent or polyvalent anion; M is a viable cation; b = number required to balance the charge; each x is independent of 3 to 1000; each c is independently 0 or 1; each h is independently 1 to 8; each q is independent of 0 to 6; each n is independent of 1 to 20; each r is independent of 0 to 20 and each t is independent of 0 to 1.

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

worin

• – jedes R₂ unabhängig ausgewählt ist aus H und C₁-C₄-Alkyl;
• – jedes R_c
  
  ist, 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, C₇-C₂₀-Alkoxy-2-hydroxyalkyl, C₇-C₂₀-Alkylaryloxy-2-hydroxyalkyl, (R₄)₂N-Alkyl, (R₄)₂N-2-Hydroxyalkyl, (R₄)₃N-Alkyl, (R₄)₃N-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 ist, das ausgewählt ist aus der Gruppe bestehend aus Na, K, 1/2Ca, und 1/2Mg;
jedes x von 0 bis 5 ist und
jedes y von 1 bis 5 ist und
mit der Maßgabe, dass:

• – der Grad der Substitution für die Gruppe R_H zwischen 0,005 und 0,1 liegt, mehr bevorzugt zwischen 0,005 und 0,05 und am meisten bevorzugt zwischen 0,01 und 0,05;
• – der Grad der Substitution für die Gruppe R_C, worin Z für H oder M steht, zwischen 0,2 und 2,0, mehr bevorzugt zwischen 0,3 und 1,0 und am meisten bevor zugt zwischen 0,4 und 0,7 liegt;
• – falls irgendein R_H eine positive Ladung trägt, diese durch ein ge eignetes 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.

Cellulosic polymer or oligomer materials suitable for use in laundry processes and providing the desired appearance and tear resistance benefits of fabrics may be characterized by the following general formula:

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

wherein

• Each R _{2 is} independently selected from H and C ₁ -C ₄ alkyl;
• - each R _c
  
  is 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 ₇ -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 / 2Ca, and 1 / 2Mg;
every x is from 0 to 5 and
every y is from 1 to 5 and
with the proviso that:

• The degree of substitution for the group R _{H is} between 0.005 and 0.1, more preferably between 0.005 and 0.05, and most preferably between 0.01 and 0.05;
• The degree of substitution for the group R _C , wherein Z is H or M, is between 0.2 and 2.0, more preferably between 0.3 and 1.0 and most preferably between 0.4 and 0, 7 lies;
• If any R _H carries a positive charge, it is balanced 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 polymer, oligomer or copolymer materials as defined above Cycloamine base can, together with polymers or oligomers based on hydrophobically modified Cellulose, as a washing solution additive either in granular or more fluid Form to be used. Alternatively, they may be granular detergents mixed in liquid Detergent compositions dissolved or a fabric softening composition.

The relationship based on the polymer, oligomer or copolymer materials from hydrophobically modified cellulose to those based on Cycloamine is in the range of 1000: 1 to 1: 1000 and is preferably between 100: 1 to 50: 1, more preferably between 50: 1 to 1: 1, and more preferably between 10: 1 to 1: 1.

The Laundry detergent compositions herein comprise from 1% to 80% by weight detergent surfactant, from 0.01% to 80% by weight organic or inorganic detergent builder and from 0.01% by weight to 5% by weight of the mixture of the polymer according to the invention, Oligomer or copolymer fabric-treating agent based on cycloamine and inventive polymer or copolymer fabric-treating agent based on hydrophobically modified Cellulose. In the detergent surfactants and detergent builder materials it can be any of those in conventional Laundry detergent products useful are.

The aqueous solutions the mixture of polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobically modified Celluloses of the present invention comprise from 0.01% by weight to 80 wt .-% of the mixture dissolved in water polymer oligomer or Copolymer solid processing agent cycloamine based and polymer or oligomer fabric treatment materials based on hydrophobically modified cellulose and other ingredients, like stabilizers and pH regulators.

In In its method aspect, the present invention relates to washing or the treatment of fabrics and textiles in aqueous Washing or treatment solutions, those from effective amounts of the detergent compositions herein are formed or from the individual components of these compositions are formed. The washing of fabrics and textiles in such Washings, followed by rinsing and drying, impart the fabric and fabric articles thus treated a better fabric appearance. These improvements can be overall improved appearance, reduction of pills / lint, reduced fade, improved abrasion resistance and / or better softness. It became surprising found that a mixture of polymers, oligomers or Cycloamine-based copolymers and polymers or oligomers Basis of hydrophobically modified cellulose according to this invention gives a better look and better tear resistance than this to reach with the appropriate amount of one of the ingredients alone would.

DETAILED DESCRIPTION OF THE INVENTION

As be said when fabrics or textiles washed in washing solutions which are the mixture of polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobic modified cellulose according to the invention include improving the appearance and tear strength of the fabrics. The mixture of polymers, oligomers or copolymers based on cycloamine and Polymers or oligomers based on hydrophobically modified cellulose can the washing solution be added by adding them to a detergent composition, incorporated into a fabric softener or separately added to the wash solution. The blends of polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobically modified Celluloses are described herein primarily as liquid or granular detergent additives, however, the invention should not be so limited. The mix out Polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobically modified cellulose, components the detergent composition, optional ingredients for such Compositions and methods of use for such compositions are described in detail below. All percentages relate on the weight, unless otherwise stated.

A) polymer, oligomer or cycloamine-based copolymer materials

One basic ingredient of the compositions of the present invention Invention includes one or more polymers, oligomers or copolymers based on cycloamine. It has been shown that such materials Fabrics and textiles used in aqueous washings be washed, which formed from detergent compositions which are a mixture of polymer, oligomer or copolymer fabric treatment materials cycloamine based and polymer or oligomer fabric treatment materials based on hydrophobically modified cellulose, a series conferring advantages in terms of appearance. These advantages in terms of appearance For example, an overall improved look of the washed Substances, a reduction in the formation of pills or lint, a Protection against color fading, improved abrasion resistance etc. include. The fabric treatment agents used in the compositions and methods herein based on cycloamine such benefits for to provide the appearance of the fabrics, with acceptably low or no loss of cleaning performance resulting from the laundry detergent composition, in which these materials are introduced, is provided.

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 piperadine and epihalohydrin condensates with a mixture of morpholine and epihalohydrin condensates combined to the desired To achieve fabric treatment results. In addition, the Molecular weights of the cycloamine-based fabric treatment agents vary within the mixture as in the examples below shown.

As Experts know, an oligomer is a molecule that only a few few monomer units, while polymers are much more Comprise monomer units. For the present invention is defined as oligomers have an average molecular weight of less than 1000, and polymers are molecules, which have an average molecular weight of over 1000. Copolymers are Polymers or oligomers wherein two or more dissimilar monomers 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 pimary cycloamine monomer, e.g. B. Piperadin, and a secondary one Cycloamine monomer, z. As morpholine, polymerized.

The Mixture of the detergent compositions herein of polymers, Oligomers or copolymers based on cyclic amines and polymers or oligomers based on hydrophobically modified cellulose usually from about 0.01% to 5% by weight of the detergent composition. More preferably, the mixture of polymers, oligomers or Cycloamine-based copolymers and polymers or oligomers Basis of hydrophobically modified cellulose from 0.1% by weight to 4% by weight the detergent composition, most preferably 0.75% to 3 %. As discussed above, however, if used as a washing solution additive is used, d. H. when the mixture of polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobically modified cellulose not in a detergent composition is involved, the concentration of the mixture of polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobically modified cellulose of 0.01% by weight to 5.0% by weight of the additive material. The laundry supplement also contains from 1% to 80% by weight of water.

Polymer-, Oligomer or copolymer materials based on cycloamine, which are for the Use in washing processes suitable and desired Benefits for the appearance and tear resistance can provide the substances be characterized by the general formula which in the Summary of the invention was given.

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

Preferred compounds falling within this general formula include compounds,

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

• – in denen 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

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

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

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

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

preferred Connections for the use as linker group R2 include, but are not limited to: polyepoxides, Ethylene carbonate, propylene carbonate, urea, alpha, beta-unsaturated carboxylic acids, esters of alpha, beta-unsaturated Carboxylic acids, Amides of alpha, beta-unsaturated Carboxylic acids, Anhydrides of alpha, beta-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, Chloressigsäureester, Derivatives of chloroform esters, derivatives of chloroacetic esters, Epihalohydrins, glycerol dichlorohydrins, bis (halohydrins), polyether dihalo compounds, phosgene, Polyhalogenated, functionalized glycidyl ethers and mixtures thereof. About that In addition, R2 may also comprise a reaction product formed by reaction one or more polyether diamines, alkylenediamines, polyalkylenepolyamines, Alcohols, alkylene glycols and polyalkylene glycols with alpha, beta-unsaturated Carboxylic acids, Esters of alpha, beta-unsaturated Carboxylic acids, Amides of alpha, beta-unsaturated carboxylic acids and anhydrides of alpha, beta-unsaturated carboxylic acids be, with the proviso, that the reaction products have at least two double bonds, two Carboxylic acid groups, contain 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 the group consisting of piperazine, piperadine, epichlorohydrin, Epichlorohydrinbenzyl quat, epichlorohydrin methyl quat, morpholine and Mixtures thereof.

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.

B) Polymers or oligomers based on hydrophobically modified cellulose

Of the basic ingredient of the compositions of the present invention The invention includes one or more cellulosic polymers or oligomers. It has been shown that these materials are fabrics and textiles, in aqueous washings which are formed from detergent compositions which are such cellulose-based fabric treatment materials Contain advantages in terms of appearance. Such Benefits in terms of the appearance of the fabrics, for example, a total improved appearance of the washed fabrics, a reduction the formation of pills or lint, a protection against fading of paints, improved abrasion resistance, etc. The fabric treatment materials based on cellulose, used in the compositions and methods herein can be used provide such benefits in terms of the appearance of the fabrics, with reasonably little or no loss of cleaning performance, those provided by the laundry detergent compositions becomes, in which these materials are incorporated.

As Experts know, an oligomer is a molecule that consists of only a few monomers exists while Include polymers significantly more monomer units. For the present Oligomers are defined as having an average molecular weight Molecular weight below about 1000, and polymers are molecules that have an average molecular weight of over 1000. A suitable one Type of polymer or oligomer fabric treatment material for use herein has an average molecular weight of 5,000 to 2,000,000, preferably from 50,000 to 1,000,000.

The Cellulose-based fabric treatment component of the detergent compositions herein typically comprises from 0.1% to 5% by weight of the detergent composition. More preferably, these cellulose-based fabric treatment materials include from 0.5% to 4% by weight of the detergent compositions, on most preferably from 0.75% to 3%. As discussed above the concentration of the cellulose-based ingredient when used as a Washing solution additive is used, d. H. if the fabric treatment additive is cellulose-based is not incorporated in a detergent composition, but 0.1 Wt .-% to 80 wt .-% of the additional material.

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

worin

• – jedes R₂ unabhängig ausgewählt ist aus der Gruppe, bestehend aus H und C₁-C₄-Alkyl;
• – jedes RC
  
  ist, worin jedes Z unabhängig ausgewählt ist aus der Gruppe, bestehend aus M. R₂, RC 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)₂N⁺-2-Hydroxyalkyl, C₆-C₁₂-Aryloxy-2-hydroxyalkyl,
  
• – jedes R₄ unabhängig ausgewählt ist aus H, C₁-C₂₀-Alkyl, C₅-C₇-Cylcoalkyl, 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 und (R₄)₂N⁺-Alkyl;

worin
M ein geeignetes Kation ist, ausgewählt aus der Gruppe, bestehend aus Na, K, 1/2 Ca und ½Mg;
jedes x von 0 bis 5 ist;
jedes y von 1 bis 5 ist; und
mit der Maßgabe, dass:

• – der Substitutionsgrad für die Gruppe R_H zwischen 0,0005 und 0,1, mehr bevorzugt zwischen 0,005 und 0,05 und am meisten bevorzugt zwischen 0,01 und 0,05 liegt;
• – der Substitutionsgrad der Gruppe R_C, worin Z für H oder M steht, zwischen 0,2 und 2,0, mehr bevorzugt zwischen 0,3 und 1,0 und am meisten bevorzugt zwischen 0,4 und 0,7 liegt;
• – falls irgendein R_H eine positive Ladung trägt, diese durch ein geeignetes Anion ausgeglichen wird; und
• – zwei R₄ auf dem gleichen 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 , Rc and

wherein

• Each R _{2 is} independently selected from the group consisting of H and C ₁ -C ₄ alkyl;
• - every RC
  
  is wherein each Z is independently selected from the group consisting of M. R _2, RC 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, C1-C ₂₀ alkoxy-2-hydroxyalkyl, C ₇ -C ₂₀ -Alkylaryloxy 2-hydroxyalkyl, (R ₄ ) ₂ N ⁺ -alkyl, (R ₄ ) ₂ N ⁺ -2-hydroxyalkyl, C ₆ -C ₁₂ -aryloxy-2-hydroxyalkyl,
  
• Each R _{4 is} independently selected from H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylal kyl, 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 and (R ₄ ) ₂ N ⁺ -alkyl;

wherein
M is a suitable cation selected from the group consisting of Na, K, 1/2 Ca and ½Mg;
each x is from 0 to 5;
each y is from 1 to 5; and
with the proviso that:

• The degree of substitution for the group R _{H is} between 0.0005 and 0.1, more preferably between 0.005 and 0.05, and most preferably between 0.01 and 0.05;
• The degree of substitution of the group R _C , wherein Z is H or M, is between 0.2 and 2.0, more preferably between 0.3 and 1.0, and most preferably between 0.4 and 0.7;
• If any R _H carries a positive charge, it is balanced 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 the group R _H , sometimes abbreviated herein as "DS _RH ", means the number of moles of the components of the group R _H substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six-membered ring, as in U.S. Pat Repeating unit having the above general structure shown. The "degree of substitution" for the group R _C , sometimes abbreviated herein as "DS _RC ", means the number of moles of the components of the group R _C , wherein Z is H or M substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six-membered ring as shown in the repeating 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. Of course, in addition to the required number of R _C moieties in which Z is H or M, there may be other R _C moieties in which Z is a group other than H or M, and most preferably these are also present.

The Production of the materials according to the present invention Invention is further defined in the examples below.

C) Cleaning effective surfactant

The Detergent compositions herein comprise from 1% by weight to 80% by weight of detergent surfactant. Preferably, these compositions comprise from 5% to 50% by weight Wt .-% surfactant. The cleaning active surfactants used can from anionic, nonionic, zwitterionic, ampholytic or be cationic type or can compatible Include mixtures of these types. Detersive surfactants suitable herein are disclosed in U.S. Patent No. 3,664,961, Norris, issued May 23, 1972, in U.S. Patent No. 3,919,678, Laughlin et al., issued December 30 1975, U.S. Patent No. 4,222,905, Cockrell, issued September 16 1980, and in U.S. Patent No. 4,239,659, Murphy, issued December 16 1980, described. Among all surfactants are the anionic and nonionic preferred.

The suitable anionic surfactants themselves may be of several different types 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 such as the sodium, potassium, ammonium and alkyl ammonium salts of higher fatty acids, the from about 8 to about 24 carbon atoms, and preferably from 12 to Contain 18 carbon atoms.

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, or organic sulfur reaction products having in their molecular structure an alkyl group of from about 10 to about 20 Containing carbon atoms, and having a sulfuric acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Particularly valuable are linear, straight-chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C _11-13 LAS.

Preferred nonionic surfactants are those of the formula R ₁ (OC ₂ H ₄ ) _n OH, wherein R _{1 is} a C ₁₀ -C ₁₆ -Al kylgruppe or a C ₈ -C ₁₂ -Alkylphenylgruppe, and n is from 3 to 80. Particularly preferred are condensation products of C ₁₂ -C ₁₅ alcohols with from 5 to 20 moles of ethylene oxide per mole of alcohol, eg. B. C ₁₂ -C ₁₃ alcohol, condensed with 6.5 moles of ethylene oxide per mole of alcohol.

Further suitable surfactants, including Polyhydroxy fatty acid amides and amine-based surfactants are disclosed in co-pending PCT application WO98 / 14300, released on March 25th 1999, entitled "Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith "disclosed on the September 15, 1997 in the name of Panadiker et al. was submitted.

D) detergent builder

The Detergent compositions herein may also be from 0.1% by weight to 80 wt .-% detergent builder include. Preferably, these include Compositions in liquid Form of 1% to 10% by weight of builder component. Detergent Builder are known in the art and include, for example, phosphate salts as well as various organic and inorganic non-phosphorus builders.

Water-soluble, Non-phosphorus organic builders useful herein include various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. suitable Polycarboxylates for this purpose Use is made of the polyacetal carboxylates disclosed in US Pat. No. 4,144,226, US Pat. granted on March 13th In 1979 to Crutchfield et al., And in U.S. Patent No. 4,246,495 on the 27th of March 1979 to Crutchfield et al. are described. Especially preferred Polycarboxylate builders are the oxydisuccinate and ether carboxylate builder compositions, a combination of tartrate monosuccinate and tartrate disuccinate and U.S. Patent Nos. 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 0.5 to 4.0, preferably from 1.0 to 2.4. Also preferred are aluminosilicates including zeolites. Such materials and their use are more fully discussed in Corkill et al., U.S. Patent No. 4,605,509. Also discussed in U.S. Patent No. 4,605,509 are crystalline layered silicates which are suitable for use in the detergent compositions of the invention.

E) Optional detergent ingredients

In addition to the surfactants, builders and mixtures described above Polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobically modified cellulose, the Detergent compositions of the present invention also a include any number of further optional components. These shut down conventional Detergent composition ingredients, such as enzymes and enzyme stabilizers, foam boosters or suds suppressors, Anti-tarnish and rust inhibitors, bleaching agents, soil suspending agents, Dirt repellent, germicidal Agents, pH regulators, alkalinity sources, which are not builders, hydrotropes, optical Brightener, dyes and fragrances.

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 bleach and salts thereof. Suitable examples of this class of agents shut down Magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioc one. Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, Hartman, issued on November 20, 1984; in European patent application EP-A-133,354, Banks et al., Published on February 20, 1985, and in the US patent No. 4,412,934, Chung et al., Issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as disclosed in U.S. Patent No. 4,634,551, issued January 6, 1987 Burns et al.

Inorganic peroxygen bleaches, generally in particulate form, may also be incorporated into the Detergent compositions can be used herein. Inorganic bleaches are indeed preferred. Such inorganic bleaching agents include alkali metal perborate and percarbonate materials. For example, sodium perborate (eg, mono- or tetrahydrate) can be used. Suitable inorganic bleaches may also include sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (eg, OXONE, manufactured by DuPont) may also be used. Frequently, inorganic peroxygen bleaches are coated with silicate, borate, sulfate, or water-soluble surfactants Coated percarbonate particles are available, for example, from various commercial sources, such as FMS, Solvay Interox, Tokai Denka, and Degussa.

inorganic Peroxygen bleach, e.g. As the perborates, the percarbonates, etc., are preferably combined with bleach activators, which for in situ production the peroxyacid, corresponding to the bleach activator, in aqueous solution (i.e., 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 In Mao et al., 1990, and U.S. Patent No. 4,412,934, issued to November 1983 to Chung et al. The nonanoyloxybenzenesulfonate (NOBS-) and tetraacetylethylenediamine (TAED) activators are typical and preferred. 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 containing from about 6 to about 12 carbon atoms, R ^{2 is} an alkylene containing from 1 to 6 carbon atoms, R ^{5 is} H or aryl or alkaryl containing from 1 to 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the blech activator by the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenolsulfonate.

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

A another class of suitable bleach activators includes the activators benzoxazine type described by Hodge et al. in U.S. Patent No. 4,966, 723, issued October 30, 1990, and incorporated herein by reference Reference is incorporated. See also U.S. Patent No. 4,545,784, issued to Sanderson, October 9, 1985, herein incorporated by reference and the acylcaroplactame, including Benzoyl caprolactam adsorbed in sodium perborate.

If Generally, peroxygen bleaches comprise about 2 Wt% to 30 wt% of the detergent compositions herein. More Preferably, the peroxygen bleaches comprise from 2% to 20% by weight % By weight of the compositions herein. Most preferred are Peroxygen bleach up to a level of 3% to 15% by weight the compositions herein. If used, bleach activators from 2% to 10% by weight of the detergent compositions herein include. Become frequent Activators so used that the molar ratio of bleach to activator in the range from 1: 1 to 10: 1, more preferably from 1.5: 1 to 5: 1 lies.

Further suitable bleaching agents and bleach activators are disclosed in co-pending PCT application WO98 / 14300, released on March 25th 1999, entitled "Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith "disclosed on the September 15, 1997 in the name of Panadiker et al. was submitted.

Another highly preferred optional ingredient in the detergent compositions herein is a detergent-active enzyme component. Enzymes can be incorporated into the present detergent compositions for a number of purposes, including removal of stains on Pro tain base or triglyceride base of substrates for preventing the transfer of fugitive dyes during fabric washing and for the recovery of the fabrics. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidase and mixtures thereof of any suitable origin, such as those of plant, animal, bacterial and yeast cell origin.

The preferred selection 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 are preferred.

"Detersive enzyme" as used herein means any enzyme that has a cleansing, dirt removing or otherwise beneficial effect in a laundry detergent composition having. Preferred enzymes for laundering purposes shut down, without limitation to be proteases, cellulases, lipases, amylases and peroxidases one.

enzymes are normally incorporated in detergent compositions in moderation, the one "cleaning effective Quantity "result. The term "cleaning effective Quantity " any amount that is capable of a cleansing, dirt-removing, whitening, deodorizing or refreshing effect on substrates, such as fabrics, exercise. In practical terms, typical amounts for current, im Commercially available Preparations up to 5 mg, by weight, in particular 0.01 mg to 3 mg of active enzyme per gram of detergent composition. In other words The compositions herein typically comprise 0.001% by weight. to 5 wt .-%, preferably 0.01 wt .-% to 1 wt .-% of a commercially available Enzyme preparation. Protease enzymes are available in such commercially available Preparations usually in sufficient proportions to 0.005 to 0.1 Anson units (AU) of activity to provide per gram of composition. Higher levels of active ingredient can be found in highly concentrated detergent formulations may be desired.

Cellulases useful herein include those described in U.S. Patent Nos. 4,435,307, Barbesgoard et al., March 6, 1984 and in GB-A-2075028; GB-A-2095275 and DE-OS-2247832 are disclosed. CAREZYME ^® and CELLUZYME® ^® (Novo) are especially useful. See also WO 91/17243 to Novo.

The enzyme-containing compositions herein can optionally also be used from .001 From about% to about 10%, preferably from about 0.005% to about 8% by weight, most preferably from 0.01% to 6% by weight of enzyme stabilizing system. The enzyme stabilization system may be any stabilization system which is compatible with the cleaning enzyme. Such a system may already contain the formulation in other active ingredients be, or can be added separately, z. By the developer or the manufacturers of detergent-ready enzymes. Such Stabilization systems can, for example Calcium ion, boric acid, Propylene glycol, short chain carboxylic acids, boric acids and mixtures thereof include and are for it designed different stabilization problems, depending on the type and physical nature of the detergent composition, too to solve.

The Compositions of the present invention may also include dye transfer inhibitors, such as polyvinyl pyrrolidine polymers, polyamine N-oxide polymers, copolymers from N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, Include peroxidases and mixtures thereof. These funds include usually from 0.01% to 10% by weight of the composition, preferably from 0.01% to 5% and more preferably from 0.05% to 2%.

More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula; RA _X -P; wherein P is a polymerizable unit to which an NO group may be bonded or the NO group may form part of the polymerizable unit or the NO group may be bonded to both units; A is one of the following structures: -NC (O) -, -C (O) O-, -S-, -O-, -N-, x is 0 or 1, and R is an aliphatic, ethoxylated aliphatic, aromatic , heterocyclic or alicyclic group or any combination thereof to which the nitrogen of the NO group may be bonded, or the NO group is a part of these groups. Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and their derivatives.

worin R₁, R₂, R₃ aliphatische, aromatische, heterocyclische oder alicyclische Gruppen oder Kombinationen davon sind; x, y und z 0 oder 1 sind; und der Stickstoff der N-O-Gruppe gebunden sein kann oder einen Teil einer der genannten Gruppen bilden kann. Die Aminoxideinheit der Polyamin-N-oxide besitzt einen pKa < 10, vorzugsweise einen pKa < 7, mehr bevorzugt einen pKa < 6.The NO group can be represented by the following general structures:

wherein R ₁ , R ₂ , R _{3 are} aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the NO group may be attached or may form part of one of said groups. The amine oxide moiety of the polyamine N-oxides has a pKa <10, preferably a pKa <7, more preferably a pKa <6.

each Polymer backbone may be used as long as the amine oxide polymer formed water soluble is and dye-retardant Features. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, Polyacrylates and mixtures thereof. The polymers include statistical or block copolymers where one type of monomer is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a relationship from amine to amine N-oxide from 10: 1 to 1: 1,000,000. The number the amine oxide groups present in the polyamine oxide polymer is, however, by suitable copolymerization or a suitable Degree of N-oxidation can be varied. The polyamine oxides can be used in can be obtained almost any degree of polymerization. Usually the average is Molecular weight in the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferably 5,000 to 100,000.

The most preferred polyamine N-oxide used in the compositions suitable herein is poly (4-vinylpyridine-N-oxide) with an average Molecular weight of about 50,000 and a ratio of amine to amine N-oxide of 1: 4. This preferred class of material may be referred to as "PVNO".

Further suitable color transfer inhibitors can in U.S. Patent No. 5,466,802, issued November 14, 1995 to Panadiker et al., can be found.

F) Preparation of the detergent composition

The Detergent compositions according to the invention can in liquid, pasty or more granular Form present. Such compositions can be made by combining the basic and optional ingredients in the required Concentrations in any order and by any conventional Means are produced. The above description for the uses the mixture of polymers, oligomers or copolymers defined herein based on cycloamine and polymers or oligomers based on hydrophobic modified cellulose should be exemplary, and professionals will recognize other uses that are also in the area of present invention.

Granular compositions are prepared, for example, by adding ganulöse components, z. As surfactants, builder, water, etc., combined as a slurry and the resulting slurry to a lower level of residual moisture (5 - 12%) spray-dried. The remaining dry Ingredients, eg. B. granules of the basic mixture of polymers, Oligomers or copolymers based on cycloamine and polymers or Oligomers based on hydrophobically modified cellulose, the spray-dried Granules in the form of granular Powder mixed in a mixing drum. The liquid components, z. B. Solutions the basic blend of polymers, oligomers, enzymes, binders and fragrances, can be sprayed on the resulting granules, to form the finished detergent composition. Granular compositions according to the present Invention can also in "compact Form ", d. H. you can a relatively higher density have as conventional ganulöse Detergent, d. H. from 550 to 950 g / l. Included in this case the granular detergent compositions according to the invention a lower amount of "inorganic Filling salt "compared to usual granular detergents; As a rule, the filling salts are around Alkaline earth metal salts of sulphates and chlorides, usually sodium sulphates; Include "compact" detergents usually not more than 10% filling salt.

Liquid detergent compositions can be prepared by mixing their basic and optional ingredients together in any desired order to provide compositions containing the components in the required concentrations. Liquid compositions according to the invention may also be in "compact form", in which case the liquid detergent compositions of the invention contain a smaller amount of water compared to conventional liquid detergents Cyclo-amine based copolymers and hydrophobically modified cellulose-based polymers or oligomers to the liquid detergent or other aqueous compositions of the invention can be accomplished by subjecting the desired mixture of polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobic Simply mix cellulose into the liquid solutions.

The Also disclosed so far are methods and compositions be applied to the production of particles as one the ingredients of detergent granules in a granular detergent composition can be used.

G) fabric washing process

The The present invention also provides a method of washing Prepared in a manner through which the substances through the Mixture of polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobically modified Cellulose is given a better appearance. In such a procedure These substances will give me an aqueous wash solution which is selected from an effective amount of the above is formed detergent composition or from the individual components of these compositions is formed. The contact of the substances with washing solutions is generally under agitation conditions, although the compositions of the present invention also for non-agitated aqueous soaking solutions for fabric cleaning and treatment can be used.

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 granular Detergent compositions are preferably from 500 to 7,000 ppm, more preferably at 1000 to 3000 ppm.

H) fabric conditioning and softening

The above-described mixture of polymers, oligomers or Cycloamine-based copolymers and polymers or oligomers the basis of hydrophobically modified cellulose as constituents the laundry detergent compositions can also be used to substances and Textiles in the absence of surfactant and builder components of the detergent composition embodiments to treat and condition the invention. So can for example a fabric conditioning composition containing only the blend from polymers, oligomers or copolymers based on cycloamine and Polymers or oligomers based on hydrophobically modified Cellulose itself, or an aqueous solution of the mixture of polymers, Oligomers or copolymers based on cycloamine and polymers or Comprising oligomers based on hydrophobically modified cellulose, during the rinse cycle a conventional one household Washing method can be added to those described above Benefits for Appearance and tear resistance to give the substances.

Further suitable fabric softening agents are disclosed in co-pending PCT application WO98 / 14300, released on March 25th 1999, entitled "Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith ", filed on September 16, 1997 in the name of Panandiker et al. The Compositions of the present invention may contain at least 1% by weight, preferably from 10% by weight, more preferably from 20% by weight to 80% Wt .-%, more preferably up to 60 wt .-% of the composition one or include several fabric softening actives.

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.

EXAMPLE 1

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

The polycationic condensate is prepared by reacting imidazole and epichlorohydrin. In a round bottom flask equipped with a magnetic stirrer, condenser and thermometer is added imidazole (0.68 mol) and 95 ml of water. The solution is warmed to 50 ° C, followed by the trop by the addition of epichlorohydrin (0.68 mol). After all the epichlorohydrin is added, the temperature is raised to 80 ° C until all of the alkylating agent has been consumed. The condensate produced has a molecular weight of 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 condensate has a molecular weight from 2000 on.

EXAMPLE 3

Synthesis of the adduct of 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 is 154.8 g (1.8 mol) of piperazine and 69.6 g (0.8 mol) of morpholine and 220 ml of water. After receiving a clear solution at 40 ° C becomes, becomes the solution heated to 55 - 65 ° C, and with vigorous stirring be 185 g (2 mol) of epichlorohydrin at such a rate added that the temperature does not exceed 80 ° C. After all Epichlorohydrin is added, the reaction mixture is heated to 85 ° C until AND ALL Alkylating agent is used up (negative Preussmann test after 4 hours). 108.8 g (0.68 mol) of 25% NaOH and 40 g of water is added, and the reaction mixture is stirred for a further hour at 85 ° C. Then Another 47 g of water are added and the mixture is allowed to cool to room temperature.

EXAMPLE 4

Synthesis of the adduct Piperazine / morpholine / epi in a ratio of 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 is 154.8 g (1.8 mol) of piperazine and 69.6 g (0.8 mol) of morpholine and 220 ml of water. After receiving a clear solution at 40 ° C becomes, becomes the solution heated to 55 - 65 ° C, and with vigorous stirring be 185 g (2 mol) of epichlorohydrin at such a rate added that the temperature does not exceed 80 ° C. After all Epichlorohydrin is added, the reaction mixture is heated to 85 ° C until all Alkylating agents are used up (negative Preussmann test after 4 hours). There are 108.8 g (0.68 mol) of 25% NaOH and Add 40 g of water, and the reaction mixture is for another Hour at 85 ° C touched. Then another 47 g of water are added, and the mixture can cool to room temperature.

EXAMPLE 5

Adduct of piperazine / morpholine / epi from example 4, oxidized to 100%

233.6 g (equivalent to 1,292 moles of oxidizable nitrogen atoms) material of the above Example 4 is mixed with 22.1 g (0.276) 50% NaOH and then heated to 55 - 65 ° C. at 102.4 g (1.421 mol) of H 2 O 2 (47.2%) are added dropwise over a Period of 3.5 hours added. After the addition is complete is, the reaction mixture is 3 more hours at the same temperature held and then over Stirred at room temperature overnight. Pt / C was added, unreacted H2O2 destroyed, and the solution then filtered.

The reactant product is characterized as follows: water content 58% PH 5.6 Chloride content 1.593 mmol / g

EXAMPLE 6

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

68.8 g (1.0 mol) of imidazole and 260.6 g (3.0 mol) of piperazine are dissolved in 700.2 g of water dissolved, and at a temperature of 50-60 ° C, 370 g (4.0 mol) of epichlorohydrin added dropwise. After the addition is complete, will the reaction mixture stirred for a further 5 hours at 80 ° C.

EXAMPLE 7

Adduct of imidazole / piperazine / epi of Example 6, 100% oxidized

To 237 g of the product of the Boring example 6 (equivalent to 1,022 moles of oxidizable nitrogen atoms) are added 80.7 g (1.12 Mole) of a 47.2% solution of H2O2 in water a period of 5 hours at 40 ° C was added. After that, the Mixture heated to 50 - 60 ° C until the theoretical amount of H2O2 was consumed. Unreacted H2O2 is destroyed by Pt / C, and the solution is then filtered.

The reaction product is 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 8

Synthesis of hydrophobically modified CMC materials

The Carboxylation of cellulose for the production of CMC is a process well known to those skilled in the art is. A procedure for the preparation of the modified CMC materials of this invention is in while the CMC manufacturing process to add the material or materials, the one or more to be substituted. An example of such a method is given below. The same procedure can with the other substituent materials described herein be hexyl chloride by the relevant substituent material or the substituent materials, for example cetyl chloride, is replaced. The amount of material that the CMC manufacturing process added should be to the desired The degree of substitution can be considered by professionals in the light of following examples are easily calculated.

EXAMPLE 9

Synthesis of hexyl ether from CMC

This Example explained the preparation of a hydrophobically modified carboxymethylcellulose and is representative of the preparation of all the cellulose ether derivatives.

cellulose (20 g), sodium hydroxide (10 g), water (30 g) and ethanol (150 g) are placed in a 500ml glass reactor. The resulting alkali cellulose will be at 25 ° C for 45 minutes touched. Monochloroacetic acid (15 g) and hexyl chloride (1 g) are added and the temperature becomes 95 ° C over time elevated and at 95 ° C for 150 minutes held. The reaction is cooled to 70 ° C and then cooled to 25 ° C. A Neutralization is by adding a sufficient amount carried out on nitric acid / acetic acid to a slurry pH to get between 8 and 9. The slurry is filtered to give a To obtain hexyl ether of CMC.

EXAMPLE 10

Cellulose Polymers Used in Test Detergent Compositions Typical examples of modified cellulosic polymers for use in the liquid and granular ones described above Detergent compositions are characterized in Tables 10A and 10B. The general polymer parameters are inherent in all of these polymers while the specific chemical structures of the materials tested are listed under the specific polymer parameters.

Table 10 A General Polymer Parameters

Table 10 B Table Specific Polymer Parameters

EXAMPLE 11

The The following are idealized chemical structures for specific cycloamine-based polymers, oligomers or copolymers of the invention. Side reactions with which during the condensation is to be expected are not shown.

Table 11

EXAMPLE 12

Preparation of Granular Detergent Test Compositions

Several heavy duty granular detergent compositions are prepared containing a mixture of polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobically modified cellulose. These granular detergent compositions all have the following basic formula on Table 12

EXAMPLE 13

Preparation of a Liquid Detergent Test Composition

Several liquid heavy duty detergent compositions are prepared from a mixture of polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobically modified cellulose. These liquid detergent compositions all have the following basic formula: TABLE 13

EXAMPLE 14

Preparation of granular detergent test compositions

Several granular detergent compositions containing a mixture of polymers, oligomers or copolymers based on cycloamine and polymers or oligomers based on hydrophobically modified cellulose are prepared. Each of these granular detergent compositions has the following basic formula: Table 14

Example 15

One Detergent agglomerate, which is used as a particulate ingredient in a Detergent composition can be used according to the following Formulas and areas made. The Granalie can by the professionals known agglomeration processes are produced, of which some are described in the present invention.

Claims (10)

A detergent composition characterized by: a) from 1 to 80% by weight of surfactants selected from the group consisting of nonionic, anionic, cationic, amphoteric zwitterionic surfactants and mixtures thereof, and b) at least 0.01% by weight, preferably at least 0.1 wt.%, most preferably at least 0.5 wt.%, and not more than 50 wt.%, preferably not more than 25.0 wt.%, most preferably not more than 5 , 0 wt .-%, a mixture of polymers, oligomers or copolymers based on cycli cellulosic amines and hydrophobically modified polymers or oligomers, wherein the ratio of hydrophobically modified polymers, oligomers or copolymers based on cellulose to those based on cyclic amines in the range of 1000: 1 to 1: 1000. A detergent composition according to claim 1, wherein the hydrophobically modified polymers or oligomers based on cellulose have the following general 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; - every R _c is

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, C ₆ -C ₁₂ -acyloxy-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 and (R ₄ ) ₂ N ^⊕ -alkyl; wherein: M is a suitable cation selected from the group consisting of Na, K, 1 / 2Ca and 1 / 2Mg; each x is 0 to 5; each y is from 1 to 5, and provided that: - the degree of substitution of the group R _{h is} between 0.0005 and 0.1, more preferably between 0.005 and 0.05 and most preferably between 0.01 and 0.05; The degree of substitution of the group R _C , wherein Z is H or M, is between 0.2 and 2.0, more preferably between 0.3 and 1.0 and most preferably between 0.4 and 0.7; If an R _H carries a positive charge, it is balanced by a suitable anion; and - two R ₄ s on the same nitrogen together can form a ring structure selected from the group consisting of piperidine and morpholine. A detergent composition according to any one of claims 1-2, wherein the polymers, oligomers or copolymers based on cyclic amines have 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, - (CH ₂ ) _h COOM, - (CH ₂ ) _h SO ₃ M, CH ₂ CH (OH) SO ₃ M, - (CH ₂ ) _h OSO ₃ M,

Wherein W is characterized by at least one cyclic moiety selected from the group consisting of:

wherein W, in addition to the at least one cyclic constituent, 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 groups, 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 hydrocarbyl moiety, the hydrocarbon moiety may comprise 2 to 4 branch units of the following general structure:

Each R ₃ is independently selected from the group consisting of H, O, R ₂ , 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, - (CH ₂ ) _h COOM, - (CH ₂ ) _h SO ₃ M, CH ₂ CH (OH) SO ₃ M, - (CH ₂ ) _h OSO ₃ M,

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 di- or polyvalent anion; M is a compatible cation; b = value required for charge equalization; each x independently stands for 3 to 1000; each c is independently 0 or 1; each h is independently 1 to 8; each q is independently 0 to 6; each n is independently 1 to 20; each r independently represents 0 to 20 and each t independently represents 0 to 1. A detergent composition according to claim 3, wherein each R _{1 is} H and at least one W is selected from the group consisting of:

A detergent composition according to any one of claims 3-4, wherein each R _{1 is} H and at least one W is selected from the group consisting of:

A detergent composition according to any one of claims 3-5, wherein each R _{1 is} H and at least one W is selected from the group consisting of:

A detergent composition according to any one of claims 1-6, wherein 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-2Hydroxyalkyl and C ₆ -C ₁₂ aryloxy-2-hydroxyalkyl. Detergent additive composition characterized by: a) from 1 to 80% by weight of water; and b) 0.01 to 5.0 wt .-%, preferably 0.1 to 4.0 wt .-%, of a mixture from polymers, oligomers or copolymers based on cyclic Amines and hydrophobically modified polymers or oligomers Cellulose. A detergent composition according to any one of claims 1-7, wherein the composition further by an inorganic peroxygen bleaching compound which is preferably selected from the group consisting from alkali metal salts of perborate, percarbonate and mixtures and a bleach activator, preferably nonanoyloxybenzenesulfonate represents. A detergent composition according to any one of claims 1-7, wherein the composition is further characterized by a cellulase enzyme is.