EP3545066B1 - Cleaning agent compositions containing copolymer - Google Patents

Description

The present invention relates to cleaning compositions containing one or more copolymers (polymer additives) which contain cationic (A) and macromonomeric (B) structural units and structural units (C), as well as one or more surfactants and water. The invention further relates to the use of the cleaning compositions or the copolymers for treating hard surfaces, for example to achieve a cleaning effect on the surface, to impart hydrophilic properties to the surface, to create shine on the surface, to achieve permanent properties such as "anti-stain", "anti-trace" or "anti-streak" on the surface or to achieve a repair effect on the surface. The invention further relates to a method for treating or cleaning a hard surface using the cleaning compositions or the copolymers.

Commercial cleaning formulations allow the efficient cleaning of industrial, domestic or public hard surfaces. They generally consist of an aqueous solution of surfactants, in particular non-ionic and anionic surfactants, alcohol(s) to facilitate drying, bases to adjust the pH and, where appropriate, quaternary amines as disinfectants.

WO 2013/170001 and WO 2013/170002 describe cleaning formulations containing alkoxylated polyethyleneimine polymers that improve the gloss on hard surfaces.

WO 2009/156067 describes cleaning formulations containing graft copolymers of saccharides that can be used to improve the gloss retention of hard surfaces and/or have hydrophilizing properties.

WO 2003/031546 describes aqueous antimicrobial cleaning compositions for the treatment of hard surfaces, with the result of maintaining or improving the gloss of the hard surfaces.

WO 98/49263 describes aqueous, acidic surface cleaners that contain a polymer additive and achieve an improved surface shine.

US2014/0005095 describes cleaning compositions for hard surfaces that achieve a shiny, streak-free surface.

EP1196523B1 describes cleaning compositions intended for the treatment of hard surfaces in industry, the home or the general public and aimed in particular at imparting hydrophilic and protective properties to these surfaces.

US 2013/0303425 A1 describes cleaning agents for hard surfaces containing a polymer comprising modified and partially quaternized polyethyleneimines into which ethylene oxide units are incorporated.

US 2007/110699 A1 discloses compositions for cleaning surfaces containing a zwitterionic polymer.

US 6 482 793 B1 describes liquid cleaning compositions for hard surfaces containing polyalkoxylene glycols and vinylpyrrolidone (co)polymers.

EP 0 467 472 A2 discloses an aqueous composition for cleaning hard surfaces containing a cationic, quaternized polymer, preferably based on beta(trialkylammonium)ethyl methacrylate.

US 2014/0378639 A1 describes water-soluble copolymers used for cosmetics and detergents.

Although good results can already be achieved with the known systems, there is still a lot of room for improvement. A major shortcoming of these cleaning formulations is that after drying, residues of the cleaning formulation can be seen on the hard surface in the form of streaks, smears or spots, which minimizes the shine of the surface.

The object of the present invention was to develop polymer additives which are water-soluble or water-dispersible and can be added to cleaning agent compositions, and thus to provide cleaning agent compositions, in particular with the result that after their application to hard surfaces, advantageous gloss effects can be observed on the hard surfaces.

• Z1) ein oder mehrere Copolymere enthaltend
  1. a) 0,1 bis 99,8 Mol-%, vorzugsweise 25,0 bis 80,0 Mol-% und besonders bevorzugt 25,0 bis 77,6 Mol-%, einer oder mehrerer kationischer Struktureinheiten (A),
  2. b) 0,1 bis 99,8 Mol-%, vorzugsweise 0,4 bis 4,5 Mol-% und besonders bevorzugt 0,5 bis 4,4 Mol-%, einer oder mehrerer makromonomerer Struktureinheiten (B) und
  3. c) 0,1 bis 99,8 Mol-% einer oder mehrerer Struktureinheiten (C), die sich von den Struktureinheiten (A) und (B) unterscheiden,
  dadurch gekennzeichnet, dass die eine oder mehreren kationischen Struktureinheiten (A) durch die folgenden allgemeinen Formeln (I) und/oder (II) repräsentiert werden:
  
  
  worin

  R1 und R1a

  jeweils gleich oder verschieden sind und unabhängig voneinander jeweils für Wasserstoff und/oder einen Methylrest stehen,

  R1b, R3, R4 und R5

  jeweils gleich oder verschieden sind und unabhängig voneinander jeweils durch Wasserstoff, einen aliphatischen Kohlenwasserstoffrest mit 1 bis 20, vorzugsweise 1 bis 4, C-Atomen, einen cycloaliphatischen Kohlenwasserstoffrest mit 5 bis 20, vorzugsweise 5 bis 8, C-Atomen, einen Arylrest mit 6 bis 14 C-Atomen und/oder Polyethylenglykol (PEG) repräsentiert werden, vorzugsweise jeweils gleich oder verschieden sind und unabhängig voneinander jeweils durch Wasserstoff und/oder Methyl repräsentiert werden und besonders bevorzugt jeweils Methyl bedeuten,

  Y

  gleich oder verschieden ist und durch Sauerstoff, NH und/oder NR³ repräsentiert wird,

  V

  gleich oder verschieden ist und durch -(CH₂)_x-,

  

  repräsentiert wird,

  x

  gleich oder verschieden ist und durch eine ganze Zahl von 1 bis 6 repräsentiert wird,

  X und X1

  jeweils gleich oder verschieden sind und unabhängig voneinander jeweils durch ein Halogenatom, C₁- bis C₄-Alkylsulfat und/oder C₁- bis C₄-Alkylsulfonat repräsentiert werden,

  und die eine oder die mehreren makromonomeren Struktureinheiten (B) durch die allgemeine Formel (III) repräsentiert werden:
  
  worin

  Rx

  gleich oder verschieden ist und durch H und/oder Methyl repräsentiert wird,

  Z

  gleich oder verschieden ist und durch C=O und/oder O(CH₂)₄ repräsentiert wird und vorzugsweise O(CH₂)₄ ist,

  I

  im molaren Mittel, eine Zahl von 0 bis 7 und vorzugsweise von 0 bis 6 ist, und

  p

  im molaren Mittel, eine Zahl von 1 bis 150, vorzugsweise von 11 bis 150 und besonders bevorzugt von 12 bis 150 ist,

  und die eine oder die mehreren Struktureinheiten (C) das Polymerisationsprodukt mindestens einer Monomerspezies ausgewählt aus der Gruppe bestehend aus nicht-kationischen Acrylamiden, nicht-kationischen Methacrylamiden und N-Vinyl-substituierten Lactamen mit 5 bis 7 Ringatomen darstellen,
  und
• Z2) ein oder mehrere Tenside
  und
• Z3) Wasser,
  wobei die Reinigungsmittel-Zusammensetzung das eine oder die mehreren Copolymere der Komponente Z1) in einer Menge von 0,005 bis 10 Gew.-% enthält, bezogen auf das Gesamtgewicht der Reinigungsmittel-Zusammensetzung.

Surprisingly, it has been found that this object can be achieved by cleaning compositions containing

• Z1) containing one or more copolymers
  1. a) 0.1 to 99.8 mol%, preferably 25.0 to 80.0 mol% and particularly preferably 25.0 to 77.6 mol%, of one or more cationic structural units (A),
  2. b) 0.1 to 99.8 mol%, preferably 0.4 to 4.5 mol% and particularly preferably 0.5 to 4.4 mol%, of one or more macromonomeric structural units (B) and
  3. c) 0.1 to 99.8 mol% of one or more structural units (C) which differ from the structural units (A) and (B),
  characterized in that the one or more cationic structural units (A) are represented by the following general formulas (I) and/or (II):
  
  
  wherein

  R1 and R1a

  are the same or different and independently represent hydrogen and/or a methyl radical,

  R1b, R3, R4 and R5

  are each the same or different and are each independently represented by hydrogen, an aliphatic hydrocarbon radical having 1 to 20, preferably 1 to 4, C atoms, a cycloaliphatic hydrocarbon radical having 5 to 20, preferably 5 to 8, C atoms, an aryl radical having 6 to 14 C atoms and/or polyethylene glycol (PEG), are preferably each the same or different and are each independently represented by hydrogen and/or methyl and are particularly preferably each methyl,

  Y

  is the same or different and is represented by oxygen, NH and/or NR ³ ,

  V

  is the same or different and is replaced by -(CH ₂ ) _x -,

  

  is represented,

  x

  is the same or different and is represented by an integer from 1 to 6,

  X and X1

  are each the same or different and are each independently represented by a halogen atom, C ₁ to C ₄ alkyl sulfate and/or C ₁ to C ₄ alkyl sulfonate,

  and the one or more macromonomeric structural units (B) are represented by the general formula (III):
  
  wherein

  Rx

  is the same or different and is represented by H and/or methyl,

  Z

  is the same or different and is represented by C=O and/or O(CH ₂ ) ₄ and is preferably O(CH ₂ ) ₄ ,

  I

  on a molar average, is a number from 0 to 7 and preferably from 0 to 6, and

  p

  on a molar average, is a number from 1 to 150, preferably from 11 to 150 and particularly preferably from 12 to 150,

  and the one or more structural units (C) represent the polymerization product of at least one monomer species selected from the group consisting of non-cationic acrylamides, non-cationic methacrylamides and N-vinyl-substituted lactams having 5 to 7 ring atoms,
  and
• Z2) one or more surfactants
  and
• Z3) Water,
  wherein the cleaning composition contains the one or more copolymers of component Z1) in an amount of 0.005 to 10 wt.%, based on the total weight of the cleaning composition.

• Z1) ein oder mehrere Copolymere enthaltend
  1. a) 0,1 bis 99,8 Mol-%, vorzugsweise 25,0 bis 80,0 Mol-% und besonders bevorzugt 25,0 bis 77,6 Mol-%, einer oder mehrerer kationischer Struktureinheiten (A),
  2. b) 0,1 bis 99,8 Mol-%, vorzugsweise 0,4 bis 4,5 Mol-% und besonders bevorzugt 0,5 bis 4,4 Mol-%, einer oder mehrerer makromonomerer Struktureinheiten (B) und
  3. c) 0,1 bis 99,8 Mol-% einer oder mehrerer Struktureinheiten (C), die sich von den Struktureinheiten (A) und (B) unterscheiden,
  dadurch gekennzeichnet, dass die eine oder mehreren kationischen Struktureinheiten (A) durch die folgenden allgemeinen Formeln (I) und/oder (II) repräsentiert werden:
  
  
  worin

  R1 und R1a

  jeweils gleich oder verschieden sind und unabhängig voneinander jeweils für Wasserstoff und/oder einen Methylrest stehen,

  R1b, R3, R4 und

  R⁵ jeweils gleich oder verschieden sind und unabhängig voneinander jeweils durch Wasserstoff, einen aliphatischen Kohlenwasserstoffrest mit 1 bis 20, vorzugsweise 1 bis 4, C-Atomen, einen cycloaliphatischen Kohlenwasserstoffrest mit 5 bis 20, vorzugsweise 5 bis 8, C-Atomen, einen Arylrest mit 6 bis 14 C-Atomen und/oder Polyethylenglykol (PEG) repräsentiert werden, vorzugsweise jeweils gleich oder verschieden sind und unabhängig voneinander jeweils durch Wasserstoff und/oder Methyl repräsentiert werden und besonders bevorzugt jeweils Methyl bedeuten,

  Y

  gleich oder verschieden ist und durch Sauerstoff, NH und/oder NR³ repräsentiert wird,

  V

  gleich oder verschieden ist und durch -(CH₂)_x-,

  

  repräsentiert wird,

  x

  gleich oder verschieden ist und durch eine ganze Zahl von 1 bis 6 repräsentiert wird,

  X und X1

  jeweils gleich oder verschieden sind und unabhängig voneinander jeweils durch ein Halogenatom, C₁- bis C₄-Alkylsulfat und/oder C₁- bis C₄-Alkylsulfonat repräsentiert werden,

  und die eine oder die mehreren makromonomeren Struktureinheiten (B) durch die allgemeine Formel (III) repräsentiert werden:
  
  worin

  Rx

  gleich oder verschieden ist und durch H und/oder Methyl repräsentiert wird,

  Z

  gleich oder verschieden ist und durch C=O und/oder O(CH₂)₄ repräsentiert wird und vorzugsweise O(CH₂)₄ ist,

  I

  im molaren Mittel, eine Zahl von 0 bis 7 und vorzugsweise von 0 bis 6 ist, und

  p

  im molaren Mittel, eine Zahl von 1 bis 150, vorzugsweise von 11 bis 150 und besonders bevorzugt von 12 bis 150 ist,

  und die eine oder die mehreren Struktureinheiten (C) das Polymerisationsprodukt mindestens einer Monomerspezies ausgewählt aus der Gruppe bestehend aus nicht-kationischen Acrylamiden, nicht-kationischen Methacrylamiden und N-Vinyl-substituierten Lactamen mit 5 bis 7 Ringatomen darstellen,
  und
• Z2) ein oder mehrere Tenside
  und
• Z3) Wasser,
  wobei die Reinigungsmittel-Zusammensetzung das eine oder die mehreren Copolymere der Komponente Z1) in einer Menge von 0,005 bis 10 Gew.-% enthält, bezogen auf das Gesamtgewicht der Reinigungsmittel-Zusammensetzung.

The invention therefore relates to cleaning compositions containing

• Z1) containing one or more copolymers
  1. a) 0.1 to 99.8 mol%, preferably 25.0 to 80.0 mol% and particularly preferably 25.0 to 77.6 mol%, of one or more cationic structural units (A),
  2. b) 0.1 to 99.8 mol%, preferably 0.4 to 4.5 mol% and particularly preferably 0.5 to 4.4 mol%, of one or more macromonomeric structural units (B) and
  3. c) 0.1 to 99.8 mol% of one or more structural units (C) which differ from the structural units (A) and (B),
  characterized in that the one or more cationic structural units (A) are represented by the following general formulas (I) and/or (II):
  
  
  wherein

  R1 and R1a

  are the same or different and independently represent hydrogen and/or a methyl radical,

  R1b, R3, R4 and

  R ⁵ are each the same or different and are each independently represented by hydrogen, an aliphatic hydrocarbon radical having 1 to 20, preferably 1 to 4, C atoms, a cycloaliphatic hydrocarbon radical having 5 to 20, preferably 5 to 8, C atoms, an aryl radical having 6 to 14 C atoms and/or polyethylene glycol (PEG), preferably are each the same or different and are each independently represented by hydrogen and/or methyl and particularly preferably each is methyl,

  Y

  is the same or different and is represented by oxygen, NH and/or NR ³ ,

  V

  is the same or different and is replaced by -(CH ₂ ) _x -,

  

  is represented,

  x

  is the same or different and is represented by an integer from 1 to 6,

  X and X1

  are each the same or different and are each independently represented by a halogen atom, C ₁ to C ₄ alkyl sulfate and/or C ₁ to C ₄ alkyl sulfonate,

  and the one or more macromonomeric structural units (B) are represented by the general formula (III):
  
  wherein

  Rx

  is the same or different and is represented by H and/or methyl,

  Z

  is the same or different and is represented by C=O and/or O(CH ₂ ) ₄ and is preferably O(CH ₂ ) ₄ ,

  I

  on a molar average, is a number from 0 to 7 and preferably from 0 to 6, and

  p

  on a molar average, is a number from 1 to 150, preferably from 11 to 150 and particularly preferably from 12 to 150,

  and the one or more structural units (C) represent the polymerization product of at least one monomer species selected from the group consisting of non-cationic acrylamides, non-cationic methacrylamides and N-vinyl-substituted lactams having 5 to 7 ring atoms,
  and
• Z2) one or more surfactants
  and
• Z3) Water,
  wherein the cleaning composition contains the one or more copolymers of component Z1) in an amount of 0.005 to 10 wt.%, based on the total weight of the cleaning composition.

The term "hard surface" in the sense of the invention means a surface made of dimensionally stable materials, e.g. plastic, ceramic, stone such as natural stone, porcelain, glass, wood, linoleum and metal such as stainless steel, typically surfaces in the kitchen and sanitary area, for example in kitchens, bathrooms and toilets, in the home but also in the industrial area, for example in butcher shops, slaughterhouses, dairies, storage tanks for food or industrial products, as well as in the public area, such as building facades, in swimming pools or in train stations.

WO 2012/076365 A1 discloses cationic copolymers containing cationic structural units and macromonomeric structural units and their use as additives for building material systems, in particular based on calcium sulfate.

WO 2008/049549 A2 describes hydrophobically modified cationic copolymers which have at least three different structural units and of which one structural unit has a terminal phenyl group or specially substituted phenyl group. With the help of the copolymers, particularly in combination with anionic surfactants, a significant improvement in water retention in aqueous building material systems based on hydraulic binders, such as cement, can be achieved even in the case of high salt loads.

In WO 2008/141844 A1 Dispersions comprising inorganic particles, water and at least one water-soluble polymer are described. The at least one water-soluble polymer has repeating units derived from monomers having at least one quaternary ammonium group, Repeating units derived from monomers having at least one carboxy group and repeating units derived from ester monomers containing polyalkoxyalkylene groups and having a number average molecular weight in the range from 3000 g/mol to 10,000 g/mol. The dispersions can be used in particular for the production of concrete and can be processed over a very long period of time.

WO 2008/046652 A1 describes graft polymers obtainable by copolymerization of at least one specific macromonomer and at least one further monomer which has a polymerizable ethylenically unsaturated double bond and their use as dispersants, for example in pigment concentrates.

In the US 2011/0144264 A1 describes the use of substances such as polyethylene glycol or poly(ethylene-co-propylene) glycol (meth)acrylic acid esters, which can contribute to stabilization during the process of latex production by emulsion polymerization of at least one polymerizable monomer.

In JP 2008-056711 A discloses copolymers having a number average molecular weight of 5,000 to 1,000,000 which contain structural units formed by polymerization of certain cationic monomers, polyoxyalkylene-modified monomers and crosslinkable monomers and which may additionally contain further structural units formed by polymerization of further monomers which can be copolymerized with the aforementioned monomers. The copolymers can be used, for example, as antistatic agents for thermoplastic polymers.

An advantage of the invention is that the copolymers of component Z1) can be added to cleaning compositions, thereby producing a gloss effect on the hard surfaces to which they have been applied.

A further advantage of the invention is that the copolymers of component Z1) can be added to cleaning compositions and impart hydrophilic properties to the hard surfaces to which they have been applied. The contact angle between a treated surface and a drop of water or a drop of an aqueous cleaning composition can be reduced. The presence of traces or stains left on the hard surfaces by water or aqueous cleaning compositions that have come into contact with them is related to the phenomenon of contraction of the drops of water or drops of aqueous cleaning compositions when in contact with hard surfaces, which leave traces on the surfaces during subsequent drying. In addition, by reducing the contact angle between the treated surface and a drop of water, the speed of drying of the surface can be improved.

On the hard surface on which the cleaning compositions according to the invention have been applied, repair effects can also be achieved in an advantageous manner
Cleaning agent compositions according to the invention can also produce advantageous cleaning effects when applied to a hard surface.

Permanent properties such as "anti-stain", "anti-trace" or "anti-streak" can advantageously be achieved on the hard surfaces to which cleaning compositions according to the invention have been applied.

Further advantages of the invention with respect to the hard surfaces on which cleaning compositions according to the invention have been applied may be, for example, as follows: the re-soiling of the surfaces can be reduced and the re-cleaning of the surface can be made easier. By treating a hard surface with cleaning agent compositions according to the invention, grease residues and lime soap residues can be advantageously removed and limescale can also be advantageously removed and new limescale deposits reduced. The formation of a biofilm on the surfaces can also be minimized or prevented and rinsing the surfaces can be made easier.

The cleaning agent compositions according to the invention or the copolymers of component Z1) can be applied in such a way that they remain on the hard surface after application ("leave on" application) or are removed from it and preferably rinsed off with water ("rinse off" application).

The cleaning compositions according to the invention or the copolymers of component Z1) can be used advantageously, for example, on hard surfaces in bathrooms or kitchens, on floors or in toilets.

Preferably, the one or more cationic structural units (A) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention represent the polymerization product of at least one monomer species selected from the group consisting of [2-(acryloyloxy)ethyl]trimethylammonium chloride, [2-(acryloylamino)ethyl]trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium methosulfate, [2-(methacryloyloxy)ethyl]trimethylammonium chloride or methosulfate, [3-(acryloylamino)propyl]trimethylammonium chloride, [3-(methacryloylamino)propyl]trimethylammonium chloride and diallyldimethylammonium chloride (DADMAC), particularly preferably, the one or more cationic structural units (A) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention represent the polymerization product of at least one monomer species selected from the group consisting of [3-(acryloylamino)-propyl]-trimethylammonium chloride, [3-(methacryloylamino)-propyl]-trimethylammonium chloride and diallyldimethylammonium chloride and particularly preferably the one or more cationic structural units (A) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention represent the polymerization product of at least one monomer species selected from the group consisting of [3-(methacryloylamino)-propyl]-trimethylammonium chloride and diallyldimethylammonium chloride.

Preferably, the one or more macromonomer structural units (B) of the formula (III) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention represent the polymerization product of at least one monomer species selected from the group consisting of polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether (wherein I, on a molar average, is a number from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 6), polyethylene glycol (meth)acrylate and polyethylene glycol-co-polypropylene glycol (meth)acrylate (wherein I, on a molar average, is a number from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 6).

In the context of the present invention, the term "(meth)acrylate" encompasses both the corresponding acrylate compound and the corresponding methacrylate compound.

1. i) R^x H, I = 0 und p, im molaren Mittel, eine Zahl von 1 bis 150, vorzugsweise von 11 bis 150 und besonders bevorzugt von 12 bis 150, wenn Z O(CH₂)₄ bedeutet oder
2. ii) R^x gleich oder verschieden und wird durch H und/oder Methyl repräsentiert, I, im molaren Mittel, eine Zahl von 1 bis 7, vorzugsweise von 2 bis 6 und besonders bevorzugt von 3 bis 6 und p, im molaren Mittel, eine Zahl von 1 bis 150, vorzugsweise von 11 bis 150 und besonders bevorzugt von 12 bis 150, wenn Z C=O bedeutet.

Particularly preferred in the one or more macromonomer structural units (B) of the formula (III) of the one or more copolymers of component Z1) of the cleaning compositions according to the invention

1. i) R ^x H, I = 0 and p, on a molar average, is a number from 1 to 150, preferably from 11 to 150 and particularly preferably from 12 to 150, when ZO(CH ₂ ) ₄ is or
2. ii) R ^x is the same or different and is represented by H and/or methyl, I, on average molar, is a number from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 6 and p, on average molar, is a number from 1 to 150, preferably from 11 to 150 and particularly preferably from 12 to 150 when Z is C=O.

• 0,1 bis 99,8 Mol-% der einen oder der mehreren Struktureinheiten (A), 0,1 bis 99,8 Mol-% der einen oder der mehreren Struktureinheiten (B) und 0,1 bis 99,8 Mol-% der einen oder der mehreren Struktureinheiten (C) enthalten,
• bevorzugt 25,0 bis 80,0 Mol-% der einen oder der mehreren Struktureinheiten (A), 0,4 bis 4,5 Mol-% der einen oder der mehreren Struktureinheiten (B) und 15,5 bis 74,6 Mol-% der einen oder der mehreren Struktureinheiten (C) enthalten, und insbesondere bevorzugt 25,0 bis 77,6 Mol-% der einen oder der mehreren Struktureinheiten (A), 0,5 bis 4,4 Mol-% der einen oder der mehreren Struktureinheiten (B) und 18,0 bis 74,5 Mol-% der einen oder der mehreren Struktureinheiten (C) enthalten.

The one or more copolymers of component Z1) of the cleaning compositions according to the invention contain/contain, in addition to the structural units (A) and (B), one or more structural units (C) which differ from the structural units (A) and (B) and wherein the one or more copolymers

• 0.1 to 99.8 mol% of the one or more structural units (A), 0.1 to 99.8 mol% of the one or more structural units (B) and 0.1 to 99.8 mol% of the one or more structural units (C),
• preferably 25.0 to 80.0 mol% of the one or more structural units (A), 0.4 to 4.5 mol% of the one or more structural units (B) and 15.5 to 74.6 mol% of the one or more structural units (C), and particularly preferably 25.0 to 77.6 mol% of the one or more structural units (A), 0.5 to 4.4 mol% of the one or more structural units (B) and 18.0 to 74.5 mol% of the one or more structural units (C).

The one or more structural units (C) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention represent the polymerization product of at least one monomer species selected from the group consisting of non-cationic acrylamides, non-cationic methacrylamides and N-vinyl-substituted lactams having 5 to 7 ring atoms.

worin

R1

gleich oder verschieden ist und Wasserstoff und/oder Methyl bedeutet, und

R3 und R4

jeweils gleich oder verschieden sind und unabhängig voneinander jeweils durch Wasserstoff, einen aliphatischen Kohlenwasserstoffrest mit 1 bis 20, vorzugsweise 1 bis 4, C-Atomen, einen cycloaliphatischen Kohlenwasserstoffrest mit 5 bis 20, vorzugsweise 5 bis 8, C-Atomen, einen Arylrest mit 6 bis 14 C-Atomen, einen Alkylarylrest mit 7 bis 14 C-Atomen, eine verzweigte oder unverzweigte C₁-C₅-Monohydroxyalkylgruppe und/oder Polyethylenglykol (PEG) repräsentiert werden

worin

R11

gleich oder verschieden ist und repräsentiert wird durch H und/oder Methyl;

X

gleich oder verschieden ist und repräsentiert wird durch NH-(C_nH_2n) mit n = 1, 2, 3 oder 4; und

R13

gleich oder verschieden ist und repräsentiert wird durch OH, N(CH₃)₂, SO₃H, PO₃H₂, O-PO₃H₂ und/oder para-substituiertes C₆H₄-SO₃H.

Preferably, the one or more structural units (C) of the one or more copolymers of the component
Z1) the cleaning compositions according to the invention selected from the Group consisting of the polymerization product of at least one N-vinyl-substituted lactam having 5 to 7 ring atoms and the structural units of the following general formulas (IV) and/or (V):

wherein

R1

is the same or different and is hydrogen and/or methyl, and

R3 and R4

are each the same or different and are each independently represented by hydrogen, an aliphatic hydrocarbon radical having 1 to 20, preferably 1 to 4, C atoms, a cycloaliphatic hydrocarbon radical having 5 to 20, preferably 5 to 8, C atoms, an aryl radical having 6 to 14 C atoms, an alkylaryl radical having 7 to 14 C atoms, a branched or unbranched C ₁ -C ₅ monohydroxyalkyl group and/or polyethylene glycol (PEG)

wherein

R11

is the same or different and is represented by H and/or methyl;

X

is the same or different and is represented by NH-(C _n H _2n ) with n = 1, 2, 3 or 4; and

R13

is the same or different and is represented by OH, N(CH ₃ ) ₂ , SO ₃ H, PO ₃ H ₂ , O-PO ₃ H ₂ and/or para-substituted C ₆ H ₄ -SO ₃ H.

Among the polymerization product selected from N-vinyl-substituted lactams having 5 to 7 ring atoms, the polymerization product of N-vinylpyrrolidone is preferred.

The groups SO ₃ H, PO ₃ H ₂ , O-PO ₃ H ₂ and para-substituted C ₆ H ₄ -SO ₃ H in the structural units of the formula (V) can also be present in salt form, preferably as NH ₄ ⁺ -, alkali or alkaline earth salt and particularly preferably as NH ₄ ⁺ - or as Na ⁺ -salt.

Among the structural units of formula (V) in which R ¹³ is N(CH ₃ ) ₂ , preferred structural units are those which represent the polymerization product of at least one monomer species selected from the group consisting of [3-(methacryloylamino)-propyl]-dimethylamine (R ¹¹ = methyl; X = NH-(C _n H _2n ) with n = 3 and R ¹³ = N(CH ₃ ) ₂ ) and [3-(acryloylamino)-propyl]-dimethylamine (R ¹¹ = H; X = NH-(C _n H _2n ) with n = 3 and R ¹³ = N(CH ₃ ) ₂ ).

Among the structural units of the formula (V), preference is given to those which represent the polymerization product of at least one monomer species selected from the group consisting of [3-(acryloylamino)propyl]dimethylamine, [3-(methacryloylamino)propyl]dimethylamine, 2-acryloylamino-2-methylpropanesulfonic acid and the salts of 2-acryloylamino-2-methylpropanesulfonic acid, and particularly preferred are those which represent the polymerization product of at least one monomer species selected from the group consisting of 2-acryloylamino-2-methylpropanesulfonic acid and the salts of 2-acryloylamino-2-methylpropanesulfonic acid. Most preferably, the one or more structural units (C) of the one or more copolymers of component Z1) of the cleaning compositions according to the invention are selected from the structural units of the general formula (IV).

Most preferably, the one or more structural units (C) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention represent the polymerization product of at least one monomer species selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-methylolacrylamide, N-isopropylacrylamide and N-tertiary butylacrylamide and more preferably, the one or more structural units (C) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention represent the polymerization product of at least one monomer species selected from the group consisting of N,N-dimethylacrylamide and N-isopropylacrylamide.

In a preferred embodiment of the invention, the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain structural units (A), (B) and (C) as repeating structural units, but beyond that no further repeating structural units.

• 23,0 bis 77,6 Mol-%, vorzugsweise 25,0 bis 77,6 Mol-%, einer oder mehrerer kationischer Struktureinheiten (A), die das Polymerisationsprodukt mindestens einer Monomerspezies ausgewählt aus der Gruppe bestehend aus [3-(Methacryloylamino)-propyl]-trimethylammoniumchlorid und Diallyldimethylammoniumchlorid darstellen,
• 0,1 bis 7,0 Mol-%, vorzugsweise 0,5 bis 4,4 Mol-%, einer oder mehrerer makromonomerer Struktureinheiten (B) der allgemeinen Formel (III), worin R^x H ist, Z O(CH₂)₄ bedeutet, I = 0 ist und p, im molaren Mittel, eine Zahl von 22 bis 150 ist, und
• 18,0 bis 74,5 Mol-% einer oder mehrerer Struktureinheiten (C), die das Polymerisationsprodukt mindestens einer Monomerspezies ausgewählt aus der Gruppe bestehend aus N,N-Dimethylacrylamid und N-Isopropylacrylamid darstellen.

In a preferred embodiment of the invention, the repeating structural units of the one or more copolymers of component Z1) of the cleaning compositions according to the invention consist of:

• 23.0 to 77.6 mol%, preferably 25.0 to 77.6 mol%, of one or more cationic structural units (A) which are the polymerization product of at least one monomer species selected from the group consisting of [3-(methacryloylamino)-propyl]-trimethylammonium chloride and diallyldimethylammonium chloride,
• 0.1 to 7.0 mol%, preferably 0.5 to 4.4 mol%, of one or more macromonomeric structural units (B) of the general formula (III), in which R ^x is H, ZO(CH ₂ ) ₄ , I = 0 and p, on a molar average, is a number from 22 to 150, and
• 18.0 to 74.5 mol% of one or more structural units (C) which represent the polymerization product of at least one monomer species selected from the group consisting of N,N-dimethylacrylamide and N-isopropylacrylamide.

• vorzugsweise 0,1 bis 99,7 Mol-% der einen oder der mehreren Struktureinheiten (A), 0,1 bis 99,7 Mol-% der einen oder der mehreren Struktureinheiten (B), 0,1 bis 99,7 Mol-% der einen oder der mehreren Struktureinheiten (C) und 0,1 bis 99,7 Mol-% der einen oder der mehreren Struktureinheiten (D) enthalten, besonders bevorzugt 25,0 bis 80,0 Mol-% der einen oder der mehreren Struktureinheiten (A), 0,4 bis 4,5 Mol-% der einen oder der mehreren Struktureinheiten (B), 15,5 bis 60,0 Mol-% der einen oder der mehreren Struktureinheiten (C) und 0,1 bis 14,6 Mol-% der einen oder der mehreren Struktureinheiten (D) enthalten, und
• insbesondere bevorzugt 25,0 bis 77,6 Mol-% der einen oder der mehreren Struktureinheiten (A), 0,5 bis 4,4 Mol-% der einen oder der mehreren Struktureinheiten (B), 18,0 bis 50,0 Mol-% der einen oder der mehreren Struktureinheiten (C) und 0,5 bis 24,6 Mol-% der einen oder der mehreren Struktureinheiten (D) enthalten.

In a further preferred embodiment of the invention, the one or more copolymers of component Z1) of the cleaning compositions according to the invention contain, in addition to the structural units (A), (B) and (C), one or more structural units (D) which differ from the structural units (A), (B) and (C), and wherein the one or more copolymers

• preferably contain 0.1 to 99.7 mol% of the one or more structural units (A), 0.1 to 99.7 mol% of the one or more structural units (B), 0.1 to 99.7 mol% of the one or more structural units (C) and 0.1 to 99.7 mol% of the one or more structural units (D), particularly preferably 25.0 to 80.0 mol% of the one or more structural units (A), 0.4 to 4.5 mol% of the one or more structural units (B), 15.5 to 60.0 mol% of the one or more structural units (C) and 0.1 to 14.6 mol% of the one or more structural units (D), and
• particularly preferably 25.0 to 77.6 mol% of the one or more structural units (A), 0.5 to 4.4 mol% of the one or more structural units (B), 18.0 to 50.0 mol% of the one or more structural units (C) and 0.5 to 24.6 mol% of the one or more structural units (D).

worin

W

gleich oder verschieden ist und durch -CO-O-(CH₂)_x repräsentiert wird,

x

eine ganze Zahl von 1 bis 6, bevorzugt 2 oder 3 ist,

R1

gleich oder verschieden ist und Wasserstoff und/oder Methyl bedeutet, und

R3 und R4

jeweils gleich oder verschieden sind und unabhängig voneinander jeweils durch Wasserstoff, einen aliphatischen Kohlenwasserstoffrest mit 1 bis 20, vorzugsweise 1 bis 4, C-Atomen, einen cycloaliphatischen Kohlenwasserstoffrest mit 5 bis 20, vorzugsweise 5 bis 8, C-Atomen, einen Arylrest mit 6 bis 14 C-Atomen und/oder Polyethylenglykol (PEG) repräsentiert werden.

If the one or more copolymers of component Z1) of the cleaning compositions according to the invention contain one or more structural units (D), in a particularly preferred embodiment of the invention they contain one or more structural units (D) selected from the structural units of the following general formula (VIII):

wherein

W

is the same or different and is represented by -CO-O-(CH ₂ ) _x ,

x

is an integer from 1 to 6, preferably 2 or 3,

R1

is the same or different and is hydrogen and/or methyl, and

R3 and R4

are each identical or different and are each independently represented by hydrogen, an aliphatic hydrocarbon radical having 1 to 20, preferably 1 to 4, C atoms, a cycloaliphatic hydrocarbon radical having 5 to 20, preferably 5 to 8, C atoms, an aryl radical having 6 to 14 C atoms and/or polyethylene glycol (PEG).

If the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain one or more structural units (D), these are selected from the structural units of the formula (VIII) in a particularly preferred embodiment of the invention.

Among the structural units of formula (VIII), preference is given to those which are the polymerization product of at least one monomer species selected from the group consisting of [2-(methacryloyloxy)ethyl]dimethylamine, [2-(acryloyloxy)ethyl]dimethylamine, [2-(methacryloyloxy)ethyl]diethylamine and [2-(acryloyloxy)ethyl]diethylamine.

worin

R11

gleich oder verschieden ist und repräsentiert wird durch H und/oder Methyl;

Z

gleich oder verschieden ist und repräsentiert wird durch O und/oder NH;

worin

R11

gleich oder verschieden ist und repräsentiert wird durch H und/oder Methyl;

Q

gleich oder verschieden ist und repräsentiert wird durch O und/oder NH;
und

R15

gleich oder verschieden ist und repräsentiert wird durch H, (C_nH_2n)-SO₃H mit n = 0, 1, 2, 3 oder 4; (C_nH_2n)-OH mit n = 0, 1, 2, 3 oder 4; (C_nH_2n)-PO₃H₂ mit n = 0, 1, 2, 3 oder 4; (C_nH_2n)-OPO₃H₂ mit n = 0, 1, 2, 3 oder 4; (C₆H₄)-SO₃H; (C₆H₄)-PO₃H₂, (C₆H₄)-OPO₃H₂ und/oder (C_mH_2m)_e-O-(A'O)_u-R¹⁶ mit m = 0, 1, 2, 3 oder 4, e = 0, 1, 2, 3 oder 4, A' = C_x'H_2x' mit x' = 2, 3, 4 oder 5, u = eine ganze Zahl von 1 bis 350 und R¹⁶ gleich oder verschieden sowie repräsentiert durch eine unverzweigte oder verzweigte C₁-C₄-Alkylgruppe.

If the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain one or more structural units (D), in a further particularly preferred embodiment of the invention they contain one or more structural units (D) selected from the structural units of the following general formulas (IX) and/or (X):

wherein

R11

is the same or different and is represented by H and/or methyl;

Z

is the same or different and is represented by O and/or NH;

wherein

R11

is the same or different and is represented by H and/or methyl;

Q

is the same or different and is represented by O and/or NH;
and

R15

is the same or different and is represented by H, (C _n H _2n )-SO ₃ H with n = 0, 1, 2, 3 or 4; (C _n H _2n )-OH with n = 0, 1, 2, 3 or 4; (C _n H _2n )-PO ₃ H ₂ with n = 0, 1, 2, 3 or 4; (C _n H _2n )-OPO ₃ H ₂ with n = 0, 1, 2, 3 or 4; (C ₆ H ₄ )-SO ₃ H; (C ₆ H ₄ )-PO ₃ H ₂ , (C ₆ H ₄ )-OPO ₃ H ₂ and/or (C _m H _2m ) _e -O-(A'O) _u -R ¹⁶ with m = 0, 1, 2, 3 or 4, e = 0, 1, 2, 3 or 4, A' = C _x' H _2x' with x' = 2, 3, 4 or 5, u = an integer from 1 to 350 and R ¹⁶ are the same or different and are represented by an unbranched or branched C ₁ -C ₄ alkyl group.

If the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain one or more structural units (D), these are selected from the structural units of the formulas (IX) and/or (X) in a further particularly preferred embodiment of the invention.

The structural units of formula (X) can also be present in salt form, preferably as NH ₄ ⁺ , alkali or alkaline earth salt and particularly preferably as NH ₄ ⁺ or as Na ⁺ salt.

Among the structural units of formulas (IX) and (X), preferred are those which represent the polymerization product of at least one monomer species selected from the group consisting of maleic anhydride, maleic acid and the salts of maleic acid.

worin

S

gleich oder verschieden ist und durch -COOM_k repräsentiert wird,

R1

gleich oder verschieden ist und repräsentiert wird durch H und/oder eine unverzweigte oder verzweigte C₁-C₄-Alkylgruppe und vorzugsweise repräsentiert wird durch H oder Methyl; und

M

ein Kation ausgewählt aus der Gruppe bestehend aus Wasserstoffion, Alkaliion und Erdalkaliion ist, mit k = Wertigkeit.

If the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain one or more structural units (D), in a further particularly preferred embodiment of the invention they contain one or more structural units (D) selected from the structural units of the following general formula (VII):

wherein

S

is the same or different and is represented by -COOM _k ,

R1

is the same or different and is represented by H and/or a straight or branched C ₁ -C ₄ alkyl group and is preferably represented by H or methyl; and

M

a cation selected from the group consisting of hydrogen ion, alkali ion and alkaline earth ion, with k = valence.

If the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain one or more structural units (D), these are selected from the structural units of the formula (VII) in a further particularly preferred embodiment of the invention.

Among the structural units of formula (VII), preferred are those which represent the polymerization product of at least one monomer species selected from the group consisting of acrylic acid, sodium acrylate, potassium acrylate, methacrylic acid, sodium methacrylate and potassium methacrylate.

worin

R11

gleich oder verschieden ist und repräsentiert wird durch H und/oder Methyl;

W

gleich oder verschieden ist und repräsentiert wird durch O;

R12

gleich oder verschieden ist und repräsentiert wird durch eine verzweigte oder unverzweigte C₁-C₅-Monohydroxyalkylgruppe;

worin

R11

gleich oder verschieden ist und repräsentiert wird durch H und/oder Methyl;

X

gleich oder verschieden ist und repräsentiert wird durch O-(C_nH_2n) mit n = 1, 2, 3 oder 4;

R13

gleich oder verschieden ist und repräsentiert wird durch OH, SO₃H, PO₃H₂, O-PO₃H₂ und/oder para-substituiertes C₆H₄-SO₃H,

worin

R14, R15 und R16

jeweils gleich oder verschieden sind und jeweils unabhängig voneinander repräsentiert werden durch H und/oder eine unverzweigte oder verzweigte C₁-C₄-Alkylgruppe;

n

gleich oder verschieden ist und repräsentiert wird durch 0, 1, 2, 3 und/oder 4;

R17

gleich oder verschieden ist und repräsentiert wird durch (C₆H₅), OH OR^y, wobei R^y eine Alkylgruppe mit 1 bis 8 und vorzugsweise 4 Kohlenstoffatomen bedeutet, und/oder -OOCCH₃.

If the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain one or more structural units (D), in a further particularly preferred embodiment of the invention they contain one or more structural units (D) selected from the structural units of the following general formulas (Va), (Vb) and/or (Vc):

wherein

R11

is the same or different and is represented by H and/or methyl;

W

is the same or different and is represented by O;

R12

is the same or different and is represented by a branched or unbranched C ₁ -C ₅ monohydroxyalkyl group;

wherein

R11

is the same or different and is represented by H and/or methyl;

X

is the same or different and is represented by O-(C _n H _2n ) with n = 1, 2, 3 or 4;

R13

is the same or different and is represented by OH, SO ₃ H, PO ₃ H ₂ , O-PO ₃ H ₂ and/or para-substituted C ₆ H ₄ -SO ₃ H,

wherein

R14, R15 and R16

are each the same or different and are each independently represented by H and/or a straight or branched C ₁ -C ₄ alkyl group;

n

is the same or different and is represented by 0, 1, 2, 3 and/or 4;

R17

is the same or different and is represented by (C ₆ H ₅ ), OH OR ^y , where R ^y is an alkyl group having 1 to 8 and preferably 4 carbon atoms, and/or -OOCCH ₃ .

If the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain one or more structural units (D), these are selected from the structural units of the formulas (Va), (Vb) and/or (Vc) in a further particularly preferred embodiment of the invention.

The groups SO ₃ H, PO ₃ H ₂ , O-PO ₃ H ₂ and para-substituted C ₆ H ₄ -SO ₃ H in the structural units of the formula (Vb) can also be present in salt form, preferably as NH ₄ ⁺ -, alkali or alkaline earth salt and particularly preferably as NH ₄ ⁺ - or as Na ⁺ -salt.

Among the structural units of formula (Vc), preferred are those which represent the polymerization product of at least one monomer species selected from the group consisting of vinyl butyl ether and vinyl acetate.

In a further preferred embodiment of the invention, the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain structural units (A), (B), (C) and (D) as repeating structural units, but beyond that no further repeating structural units.

• 15,0 bis 35,0 Mol-%, vorzugsweise 20,0 bis 30,0 Mol-%, einer oder mehrerer kationischer Struktureinheiten (A), die das Polymerisationsprodukt mindestens einer Monomerspezies ausgewählt aus der Gruppe bestehend aus [3-(Acryloylamino)-propyl]-trimethylammoniumchlorid, [3-(Methacryloylamino)-propyl]-trimethylammoniumchlorid und Diallyldimethylammoniumchlorid darstellen und vorzugsweise das Polymerisationsprodukt von [3-(Methacryloylamino)-propyl]-trimethylammoniumchlorid darstellen,
• 0,5 bis 10,0 Mol-%, vorzugsweise 2,0 bis 6,0 Mol-%, einer oder mehrerer makromonomerer Struktureinheiten (B) der allgemeinen Formel (III), vorzugsweise einer oder mehrerer makromonomerer Struktureinheiten (B) der allgemeinen Formel (III), worin R^x H ist, Z O(CH₂)₄ bedeutet, I = 0 ist und p, im molaren Mittel, eine Zahl von 22 bis 150 ist,
• 60,0 bis 80,0 Mol-%, vorzugsweise 65,0 bis 75,0 Mol-%, einer oder mehrerer Struktureinheiten (C), die das Polymerisationsprodukt mindestens einer Monomerspezies ausgewählt aus der Gruppe bestehend aus N,N-Dimethylacrylamid, N-Isopropylacrylamid, N-Vinylpyrrolidon, 2-Acryloylamino-2-methylpropansulfonsäure und den Salzen der 2-Acryloylamino-2-methylpropansulfonsäure darstellen und vorzugsweise das Polymerisationsprodukt von N,N-Dimethylacrylamid darstellen, und
• 0,1 bis 5,0 Mol-%, vorzugsweise 0,5 bis 3,0 Mol-%, einer oder mehrerer Struktureinheiten (D), die das Polymerisationsprodukt mindestens einer Monomerspezies ausgewählt aus der Gruppe bestehend aus Maleinsäureanhydrid, Maleinsäure und den Salzen der Maleinsäure darstellen.

In a preferred embodiment of the invention, the repeating structural units of the one or more copolymers of component Z1) of the cleaning compositions according to the invention consist of:

• 15.0 to 35.0 mol%, preferably 20.0 to 30.0 mol%, of one or more cationic structural units (A) which are the polymerization product of at least one monomer species selected from the group consisting of [3-(acryloylamino)propyl]trimethylammonium chloride, [3-(methacryloylamino)propyl]trimethylammonium chloride and diallyldimethylammonium chloride and preferably the polymerization product of [3-(methacryloylamino)propyl]trimethylammonium chloride,
• 0.5 to 10.0 mol%, preferably 2.0 to 6.0 mol%, of one or more macromonomeric structural units (B) of the general formula (III), preferably one or more macromonomeric structural units (B) of the general formula (III), in which R ^x is H, ZO(CH ₂ ) ₄ , I = 0 and p, on a molar average, is a number from 22 to 150,
• 60.0 to 80.0 mol%, preferably 65.0 to 75.0 mol%, of one or more structural units (C) which are the polymerization product of at least one monomer species selected from the group consisting of N,N-dimethylacrylamide, N-isopropylacrylamide, N-vinylpyrrolidone, 2-acryloylamino-2-methylpropanesulfonic acid and the salts of 2-acryloylamino-2-methylpropanesulfonic acid and preferably the polymerization product of N,N-dimethylacrylamide, and
• 0.1 to 5.0 mol%, preferably 0.5 to 3.0 mol%, of one or more structural units (D) which represent the polymerization product of at least one monomer species selected from the group consisting of maleic anhydride, maleic acid and the salts of maleic acid.

Preferably, the structural units (A), (B), (C) and optionally (D) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention are present in a random, block-shaped, alternating or gradient-like distribution in the copolymer.

Preferably, the weight-average molecular weights M _w of the one or more copolymers of component Z1) of the cleaning compositions according to the invention are from 10,000 to 250,000 g/mol, particularly preferably from 15,000 to 200,000 g/mol and especially preferably from 20,000 to 150,000 g/mol.

The copolymers of component Z1) of the cleaning agent compositions according to the invention contain repeating structural units (generally -C(R ^s1 )(R ^s2 )-C(R ^s3 )(R ^s4 )-) which represent the polymerization product of corresponding monomers with polymerizable olefinic double bonds (generally C(R ^s1 )(R ^s2 )=C(R ^s3 )(R ^s4 )). The radicals R ^s1 , R ^s2 , R ^s3 and R ^s4 are not defined in more detail here, but are only given for the sake of completeness as radicals bonded to the corresponding carbon atoms "C". The structural units (A), (B) and (C) contained in the copolymers of component Z1) and the structural units (D) optionally additionally contained in the copolymers of component Z1) are examples of such repeating structural units. Structural units which originate, for example, from radical initiators or from chain transfer regulators which may be used in the copolymerization do not represent recurring structural units. Accordingly, recurring structural units are not understood to mean, for example, terminal groups. The amounts given for the structural units (A), (B), (C) and (D) in mol% are based on the total amount of repeating structural units contained in the respective copolymers of component Z1).

The copolymers of component Z1) of the cleaning agent compositions according to the invention can be prepared by methods familiar to the person skilled in the art. The copolymers of component Z1) can particularly preferably be prepared by radical solvent polymerization. Common solvents can preferably be polar solvents such as alcohols or water, as well as alcohol-water mixtures. The polymerization is started by radical sources such as, for example, inorganic persulfates, organic azo compounds, peroxides, inorganic redox systems, or UV light. In addition, chain transfer regulators can be used which form less reactive radicals in order to control the molecular weight of the copolymers. Such chain transfer regulators are, for example, phenols, thiols, for example 2-mercaptoethanesulfonate sodium, or sodium hypophosphite. In an exemplary implementation, the monomers for producing the copolymers of component Z1) and optionally a chain transfer regulator are dissolved in the solvent, oxygen is expelled, the temperature is then increased, and the radical initiator is added. The copolymerization is then carried out at the desired temperature for the desired period of time. The reaction mixture is then cooled if necessary and the copolymer formed is either further processed in solution or worked up, e.g. the solution containing the copolymer can be concentrated by partially evaporating the solvent or the solvent can be completely removed by evaporation or the copolymer can be isolated in another way, for example by freeze-drying or precipitation.

The cleaning compositions according to the invention contain the one or more copolymers of component Z1) in an amount of 0.005 to 10% by weight, preferably in an amount of 0.01 to 5% by weight and particularly preferably in an Amount of 0.1 to 0.5 wt.%, each based on the total weight of the cleaning composition.

Component Z2)

The cleaning compositions according to the invention contain one or more surfactants as component Z2).

Preferably, the one or more surfactants of component Z2) of the cleaning compositions according to the invention are selected from the group consisting of anionic, nonionic, amphoteric and cationic surfactants.

The cleaning compositions according to the invention can optionally contain anionic surfactants, e.g. alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, alkanesulfonates, alkyl ether carboxylic acids, sulfosuccinates, isethionates, taurates, glycinates and/or acylglutamates. The alkyl chains of the surfactants mentioned can be synthetic or of natural origin and consist of 8 to 30, preferably 8 to 18 and particularly preferably 12 to 14 carbon atoms in a linear or branched arrangement.

Anionic surfactants used according to the invention are preferably aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates. Also usable within the scope of the present invention are alkylbenzenesulfonates, fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates as well as [alpha]-sulfofatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

Preferred are fatty alcohol sulfates and/or fatty alcohol ether sulfates, especially fatty alcohol sulfates. Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols, while Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to be the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the sense of the present invention preferably with longer-chain alcohols. As a rule, a complex mixture of addition products with different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. Another embodiment of the alkoxylation consists in the use of mixtures of alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Preferred fatty alcohol ether sulfates are the sulfates of low-ethoxylated fatty alcohols with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO.

Particularly preferred are alkylbenzenesulfonate, alkanesulfonate, alkyl ether sulfate or alkyl sulfate.

The anionic surfactants are usually used as salts, but also as acids. The salts are preferably alkali metal salts, alkaline earth metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or potassium salts, especially preferably sodium salts.

Other surfactants can be nonionic, amphoteric and/or cationic surfactants, for example betaines, amidobetaines, amine oxides, amidoamine oxides, fatty alcohol polyglycol ethers, alkyl polyglycosides or quaternary ammonium compounds.

Other non-ionic surfactants can be, for example, alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers (fatty alcohol alkoxylates), alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also usable are Ethylene oxide-propylene oxide block copolymers and fatty acid alkanolamides and fatty acid polyglycol ethers. Another important class of nonionic surfactants that can be used according to the invention are the polyol surfactants and here in particular the glycosurfactants, such as alkyl polyglycosides, especially alkyl polyglucosides.

Suitable fatty alcohol polyglycol ethers are unbranched or branched, saturated or unsaturated C ₈ -C ₂₂ alcohols alkoxylated with ethylene oxide (EO) and/or propylene oxide (PO) and having a degree of alkoxylation of up to 30, preferably ethoxylated C ₁₀ -C ₁₈ fatty alcohols having a degree of ethoxylation of less than 30, particularly preferably 1 to 20, especially preferably 1 to 12 and extremely preferably 1 to 8, for example C ₁₂ -C ₁₄ fatty alcohol ethoxylates with 8 EO.

Alkyl polyglycosides are surfactants that can be obtained by the reaction of sugars and alcohols according to the relevant processes of preparative organic chemistry, resulting in a mixture of monoalkylated, oligomeric or polymeric sugars depending on the type of preparation. Preferred alkyl polyglycosides are the alkyl polyglucosides, where the alcohol is particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C ₈ - C ₁₈ alkyl chains and the degree of oligomerization (DP) of the sugar is from 1 to 10, preferably from 1 to 6, particularly preferably from 1.1 to 3 and especially preferably from 1.1 to 1.7, for example C ₈ -C ₁₀ alkyl-1,5-glucoside (DP of 1.5).

The amphoteric surfactants (zwitterionic surfactants) that can be used according to the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids and biosurfactants.

Suitable betaines are the alkyl betaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI sultaines) and the amidosulfobetaines as well as the phosphobetaines. Examples of suitable betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl Betaine, Apricotamidopropylbetaine, Avocadamidopropylbetaine, Babassuamidopropylbetaine, Behenamidopropylbetaine, Behenylbetaine, Betaine, Canolamidopropylbetaine, Capryl/Capramidopropylbetaine, Carnitine, Cetylbetaine, Cocamidoethylbetaine, Cocamidopropylbetaine, Cocamidopropylhydroxysultaine, Cocobetaine, Cocohydroxysultaine, Coco/Oleamidopropylbetaine, Coco-Sultaine, Decylbetaine, Dihydroxyethyloleylglycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethylstearylglycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG-Betaine, Erucamidopropylhydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropylbetaine, Lauramidopropylbetaine, Laurylbetaine, Laurylhydroxysultaine, Laurylsultaine, Milkamidopropylbetaine, Minkamidopropylbetaine, Myristamidopropylbetaine, Myristylbetaine, Oleamidopropylbetaine, Oleamidopropylhydroxysultaine, Oleylbetaine, Olivamidopropylbetaine, Palmamidopropylbetaine, Palmitamidopropylbetaine, Palmitoyl Carnitine, Palm Kernelamidopropyl Betaine, Polytetrafluoroethylene Acetoxypropyl Betaine, Ricinoleamidopropylbetaine, Sesamidopropylbetaine, Soyamidopropylbetaine, Stearamidopropylbetaine, Stearylbetaine, Tallowamidopropylbetaine, Tallowamidopropylhydroxysultaine, Tallowbetaine, Tallowdihydroxyethylbetaine, Undecylenamidopropylbetaine and Wheat Germamidopropyl Betaine.

The amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.

Examples of suitable amine oxides are the following compounds named according to INCI: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimidine Oxide, Dihydroxyethyl C ₈ -C ₁₀ Alkoxypropylamine Oxide, Dihydroxyethyl C ₉ -C ₁₁ Alkoxypropylamine Oxide, Dihydroxyethyl C ₁₂ -C ₁₅ Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxypropyl C ₁₂ -C ₁₅ Alkoxypropylamine Oxide, Isostearamidopropylamine Oxide, Isostearamidopropyl Morpholine Oxide, Lauramidopropylamine Oxide, Lauramine Oxide, Methyl Morpholine Oxide, Milkamidopropyl Amine Oxide, Minkamidopropylamine Oxide, Myristamidopropylamine Oxide, Myristamine Oxide, Myristyl/Cetyl Amine Oxide, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopropylamine Oxide, Palmitamidopropylamine Oxide, Palmitamine Oxide, PEG-3 Lauramine Oxide, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide, Soyamidopropylamine Oxide, Stearamidopropylamine Oxide, Stearamine Oxide, Tallowamidopropylamine Oxide, Tallowamine Oxide, Undecylenamidopropylamine Oxide and Wheat Germamidopropylamine Oxide.

Examples of alkylamidoalkylamines are the following compounds named according to INCI: Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxyamphodiacetate, Disodium Stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropylsulfonate, Sodium Capryloamphopropionate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoamphopropionate, Sodium Lauroamphoacetate, Sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Wheat Germamphoacetate and Trisodium Lauroampho PG-Acetate Chloride Phosphate.

Examples of alkyl-substituted amino acids are the following compounds named according to INCI: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic Acid, DEA-Lauraminopropionate, Disodium Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, Lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C ₁₂ -C ₁₅ Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA-Lauraminopropionate and TEA-Myristaminopropionate.

Particularly preferably, the one or more surfactants of component Z2) of the cleaning compositions according to the invention are selected from the group consisting of fatty alcohol polyglycol ethers, alkyl polyglycosides, alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfates, alkyl sulfates and quaternary ammonium compounds.

The proportion of the one or more surfactants of component Z2) in the cleaning agent composition according to the invention is preferably from 0.1 to 20% by weight and particularly preferably from 0.1 to 6.0% by weight, in each case based on the total weight of the cleaning agent composition according to the invention.

Component Z3)

The proportion of water in the cleaning agent compositions according to the invention is preferably from 10.00 to 99.8% by weight, particularly preferably from 40.00 to 98.00% by weight and especially preferably from 70 to 97.00% by weight, in each case based on the total weight of the cleaning agent compositions according to the invention.

• Z4) eine oder mehrere anorganische oder organische Säuren als Komponente Z4),
• Z5) einen oder mehrere Komplexbildner als Komponente Z5),
• Z6) ein oder mehrere von Wasser verschiedene Lösungsmittel als Komponente Z6),
• Z7) ein oder mehrere weitere Additive, vorzugsweise ausgewählt aus der Gruppe bestehend aus Viskositätsreglern, Enzymen, Bleichmitteln, Konservierungsmitteln, Duftstoffen und Farbstoffen, als Komponente Z7),

und beträgt der pH-Wert der Reinigungsmittel-Zusammensetzung vorzugsweise von 1 bis 14 und besonders bevorzugt von 3 bis 11.Preferably, the cleaning compositions according to the invention contain, in addition to the one or more copolymers of component Z1), the one or more surfactants of component Z2) and water of component Z3), one or more further substances selected from components Z4), Z5), Z6) and/or Z7):

• Z4) one or more inorganic or organic acids as component Z4),
• Z5) one or more complexing agents as component Z5),
• Z6) one or more solvents other than water as component Z6),
• Z7) one or more further additives, preferably selected from the group consisting of viscosity regulators, enzymes, bleaching agents, preservatives, fragrances and dyes, as component Z7),

and the pH of the cleaning composition is preferably from 1 to 14 and particularly preferably from 3 to 11.

Component Z4)

The acids can be inorganic acids, e.g. hydrochloric acid, sulfuric acid, nitric acid, amidosulfonic acid and/or phosphoric acid.

In a preferred embodiment of the invention, the acids contained are organic acids, particularly preferably non-complexing acids such as lactic acid, formic acid, acetic acid, glycolic acid and/or gluconic acid. Other preferred acids are malic acid, citric acid, tartaric acid, adipic acid and/or succinic acid. In a preferred embodiment the cleaning compositions according to the invention contain an acid. In a further preferred embodiment of the invention, the cleaning compositions according to the invention contain a mixture of two or more acids.

The amount of acid used, if it is different from 0%, is preferably from 0.1 to 10% by weight, particularly preferably from 0.2 to 5% by weight and especially preferably from 1 to 3% by weight, in each case based on the total weight of the cleaning agent composition according to the invention.

In a further preferred embodiment of the invention, a salt of an acid can also be added to buffer the pH value, in particular the sodium, potassium or magnesium salt, but also other alkali or alkaline earth salts or ammonium salts, in particular volatile amines such as monoethanolamine, ammonia, diethanolamines, but also triethanolamine. In a particularly preferred embodiment of the invention, the salt or salts of the acid or acids already present are used.

Component Z5)

Suitable complexing agents are known to the person skilled in the art and are described by way of example in DE-A-10 2009 001 559 described.

Complexing agents (INCI Chelating Agents), also known as sequestering agents, are ingredients that can complex and inactivate metal ions in order to prevent their adverse effects on the stability or appearance of the agent, such as cloudiness. On the one hand, it is important to complex the calcium and magnesium ions of water hardness, which are incompatible with many ingredients. On the other hand, the complexing of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agent. In addition, the complexing agents support the cleaning effect.

Suitable examples are the following complexing agents designated according to INCI: Aminotrimethylene, Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxide, Ribonic Acid, Sodium Chitosan Methylene Phosphonate, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonate, Sodium Dihydroxyethylglycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA-Polyphosphate, Tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

The proportion of component Z5) in the cleaning agent composition according to the invention, if it is different from 0%, is preferably from 0.1 to 10% by weight, particularly preferably from 0.1 to 3.0% by weight and especially preferably from 0.1 to 1.0% by weight, in each case based on the total weight of the cleaning agent composition according to the invention.

Component Z6)

Suitable water-soluble solvents are known to the person skilled in the art and are described by way of example in US2005/0239674 Alcohols, glycerin, glycols and glycol ethers are preferably used, preferably lower alcohols such as ethanol, isopropanol, butanol, isobutanol or alkylene glycols, e.g. propylene glycol, and glycol ethers, e.g. ethylene glycol n-butyl ether or propylene glycol n-butyl ether.

In a preferred embodiment, mixtures of several solvents are used.

The proportion of component Z6) in the cleaning agent composition according to the invention, if it is different from 0%, is preferably from 0.1 to 10% by weight, particularly preferably from 0.1 to 3% by weight and especially preferably from 0.5 to 1.5% by weight.

Component Z7)

Suitable additives are other common ingredients of cleaning agents, for example disinfectants, pH adjusters, dyes, fragrances, buffers, viscosity regulators, corrosion inhibitors, organic and inorganic salts, optical brighteners, bleaches, antioxidants, opacifiers, hydrotropes, abrasives, preservatives, oxidizing agents and/or insecticides. These additives are well known to the person skilled in the art and are described by way of example in the DE-A-10 2009 001 559 described.

According to the invention, bleaching agents can be added to the composition. Suitable bleaching agents include peroxides, peracids and/or perborates, H ₂ O ₂ is particularly preferred.

The cleaning agent compositions according to the invention can also contain enzymes, preferably proteases, lipases, amylases, hydrolases and/or cellulases. They can be added to the cleaning agent compositions according to the invention in any form established according to the prior art. In the case of liquid or gel-like cleaning agent compositions according to the invention, these include in particular solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray drying or extrusion of the enzyme solution. together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as if in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer that is impermeable to water, air and/or chemicals. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules, for example by applying polymeric film formers, are advantageously low in dust and are stable in storage due to the coating.

Furthermore, enzyme stabilizers can be present in enzyme-containing cleaning agent compositions according to the invention in order to protect an enzyme contained in a cleaning agent composition according to the invention from damage such as, for example, inactivation, denaturation or decomposition due to physical influences, oxidation or proteolytic cleavage. The following are particularly suitable as enzyme stabilizers, depending on the enzyme used: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, such as substituted phenylboronic acids or their salts or esters; peptide aldehydes (oligopeptides with a reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerin, ethylene glycol, propylene glycol or sorbitol; as well as reducing agents and antioxidants such as sodium sulfite and reducing sugars. Other suitable stabilizers are known from the prior art.

Preferably, combinations of stabilizers are used, for example the combination of polyols, boric acid and/or borax, the combination of boric acid or borate, reducing salts and succinic acid or other Dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.

Antimicrobial active ingredients from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides are suitable according to the invention as disinfectants and/or preservatives. Preferred antimicrobial active ingredients are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-(3,4-dichlorophenyl)urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)-bis-(1-octanamine) dihydrochloride, N,N'-bis-(4-chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, antimicrobial quaternary surface-active compounds, guanidines. Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group, as for example KH Wallhäusser in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5th edition - Stuttgart; New York: Thieme, 1995 ) describes.

The terms disinfection, sanitation, antimicrobial effect and antimicrobial agent have the usual technical meaning within the scope of the invention, which is used, for example, by KH Wallhäusser in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5th edition - Stuttgart; New York: Thieme, 1995 ) is reproduced. While disinfection in the narrower sense of medical practice means the killing of - theoretically all - While sanitation means the elimination of all infectious germs as far as possible, including saprophytic germs that are normally harmless to humans.

1. (i) Copolymere von zwei oder mehr Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit C₁-₄-Alkanolen gebildeten, Ester (INCI Acrylates Copolymer), zu denen etwa die Copolymere von Methacrylsäure, Butylacrylat und Methylmethacrylat (CAS-Bezeichnung gemäß Chemical Abstracts Service: 25035-69-2 ) oder von Butylacrylat und Methylmethacrylat ( CAS 25852-37-3 ) gehören und die beispielsweise von der Firma Rohm & Haas unter den Handelsnamen Aculyn^® und Acusol^® sowie von der Firma Degussa (Goldschmidt) unter dem Handelsnamen Tego^® Polymer erhältlich sind, z. B. die anionischen nicht-assoziativen Polymere Aculyn^® 22, Aculyn^® 28, Aculyn^® 33 (vernetzt), Acusol^® 810, Acusol^® 823 und Acusol^® 830 ( CAS 25852-37-3 );
2. (ii) vernetzte hochmolekulare Acrylsäurecopolymere, zu denen etwa die mit einem Allylether der Saccharose oder des Pentaerythrits vernetzten Copolymere von C_10-30-Alkylacrylaten mit einem oder mehreren Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit C₁-C₄-Alkanolen gebildeten, Ester (INCI Acrylates/C₁₀-C₃₀ Alkyl Acrylate Crosspolymer) gehören und die beispielsweise von der Firma BFGoodrich unter dem Handelsnamen Carbopol^® erhältlich sind, z. B. das hydrophobierte Carbopol^® ETD 2623 und Carbopol^® 1382 (INCI Acrylates/C_10-30 Alkyl Acrylate Grosspolymer) sowie Carbopol^® AQUA 30 (früher Carbopol^® EX 473).

Polyacrylic and polymethacrylic compounds include, for example, high molecular weight homopolymers of acrylic acid (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association (CTFA): Carbomer) cross-linked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers. Such polyacrylic acids are available from 3V Sigma under the trade name Polygel ^® , e.g. Polygel ^® DA, and from BFGoodrich under the trade name Carbopol ^® , e.g. Carbopol ^® 940 (molecular weight approx. 4,000,000), Carbopol ^® 941 (molecular weight approx. 1,250,000) or Carbopol ^® 934 (molecular weight approx. 3,000,000). They also include the following acrylic acid copolymers:

1. (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C ₁ - ₄ alkanols (INCI Acrylates Copolymer), which include the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2 ) or butyl acrylate and methyl methacrylate ( CAS-25852-37-3 ) and which are available, for example, from Rohm & Haas under the trade names Aculyn ^® and Acusol ^® and from Degussa (Goldschmidt) under the trade name Tego ^® Polymer, e.g. the anionic non-associative polymers Aculyn ^® 22, Aculyn ^® 28, Aculyn ^® 33 (crosslinked), Acusol ^® 810, Acusol ^® 823 and Acusol ^® 830 ( CAS-25852-37-3 );
2. (ii) cross-linked high molecular weight acrylic acid copolymers, which include copolymers of C _10-30 alkyl acrylates cross-linked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with C ₁ -C ₄ -alkanols, esters (INCI Acrylates/C ₁₀ -C ₃₀ Alkyl Acrylate Crosspolymer) and which are available, for example, from BFGoodrich under the trade name Carbopol ^® , e.g. the hydrophobic Carbopol ^® ETD 2623 and Carbopol ^® 1382 (INCI Acrylates/C _10-30 Alkyl Acrylate Grosspolymer) as well as Carbopol ^® AQUA 30 (formerly Carbopol ^® EX 473).

Other thickeners are polysaccharides and heteropolysaccharides, in particular polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, e.g. propoxylated guar, and their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g. hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropylmethyl or hydroxyethylmethyl cellulose or cellulose acetate.

A particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 - 15 × 10 ⁶ and is available, for example, from Kelco under the trade names Keltrol ^® and Kelzan ^® or from Rhodia under the trade name Rhodopol ^® .

Layered silicates can also be used as thickeners. These include, for example, the magnesium or sodium-magnesium layered silicates from Solvay Alkali available under the trade name Laponite ^® , in particular Laponite ^® RD or Laponite ^® RDS, as well as the magnesium silicates from Süd-Chemie, especially Optigel ^® SH.

The amount of viscosity regulator, if it is different from 0%, is preferably up to 0.5% by weight, particularly preferably from 0.001 to 0.3% by weight, especially preferably from 0.01 to 0.2% by weight and extremely preferably from 0.01 to 0.15% by weight, in each case based on the total weight of the cleaning agent composition according to the invention. The viscosity of the cleaning agent composition according to the invention is preferably from 0.4 to 400 m•Pas.

Furthermore, the cleaning compositions according to the invention can contain one or more corrosion inhibitors.

Suitable corrosion inhibitors (INCI Corrosion Inhibitors) are, for example, the following substances named according to INCI: Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphate, Nitromethane, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrite, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate and Triisopropanolamine.

Individual fragrance compounds can be used as fragrances, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohols and hydrocarbon type. Fragrance compounds of the ester type include, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether, aldehydes include, for example, the linear alkanals with 8 to 18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, hydroxycitronellal, lilial and bourgeonal, and ketones include, for example, benzyl ethyl ether. B. the ionones, alpha-isomethylionone and methylcedryl ketone, to the alcohols anethole, citronellol, eugenol, geranion, linalol, phenylethyl alcohol and terpineol, to the Hydrocarbons mainly include terpenes and balsams. Mixtures of different fragrances are preferred, as they combine to create an appealing scent.

Natural fragrance mixtures that are available from plant or animal sources can also be used as fragrances, e.g. pine, citrus, jasmine, lily, rose or ylang-ylang oil. Essential oils with lower volatility, which are usually used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil.

The amount of fragrances in the cleaning compositions according to the invention, if different from 0%, is preferably from 0.001 to 2% by weight and particularly preferably from 0.01 to 2% by weight, based on the total weight of the cleaning compositions according to the invention.

The dyes and pigments optionally contained in the cleaning agent compositions according to the invention, both organic and inorganic dyes, can be selected from the corresponding positive list of the Cosmetics Regulation or the EC list of cosmetic colorants. Pearlescent pigments are also advantageously used, e.g. fish silver (guanine/hypoxanthine mixed crystals from fish scales) and mother of pearl (ground mussel shells), monocrystalline pearlescent pigments such as bismuth oxychloride (BiOCl), layer-substrate pigments, e.g. mica/metal oxide, silver-white pearlescent pigments made of TiO ₂ , interference pigments (TiO ₂ , different layer thicknesses), colored luster pigments (Fe ₂ O ₃ ) and combination pigments (TiO ₂ /Fe ₂ O ₃ , TiO ₂ /Cr ₂ O ₃ , TiO ₂ /Prussian blue, TiO ₂ /carmine).

The amount of dyes and pigments in the cleaning compositions according to the invention, if different from 0%, is preferably from 0.01 to 1.0% by weight, based on the total weight of the cleaning compositions according to the invention.

The proportion of component Z7) in the cleaning agent compositions according to the invention, if it is different from 0%, is preferably from 0.01 to 10% by weight, particularly preferably from 0.1 to 1% by weight and especially preferably from 0.1 to 0.5% by weight, in each case based on the total weight of the cleaning agent compositions according to the invention.

• Z1) 0,005 bis 10,00 Gew.-% der Komponente Z1),
• Z2) 0,10 bis 20,00 Gew.-% der Komponente Z2),
• Z3) 10,00 bis 99,8 Gew.-% der Komponente Z3),
• Z4) 0 bis 10 Gew.-% der Komponente Z4),
• Z5) 0 bis 10 Gew.-% der Komponente Z5),
• Z6) 0 bis 10 Gew.-% der Komponente Z6), und
• Z7) 0 bis 10 Gew.-% der Komponente Z7),

jeweils bezogen auf das Gesamtgewicht der erfindungsgemäßen Reinigungsmittel-Zusammensetzungen.The cleaning compositions according to the invention preferably contain

• Z1) 0.005 to 10.00 wt.% of component Z1),
• Z2) 0.10 to 20.00 wt.% of component Z2),
• Z3) 10.00 to 99.8 wt.% of component Z3),
• Z4) 0 to 10 wt.% of component Z4),
• Z5) 0 to 10 wt.% of component Z5),
• Z6) 0 to 10 wt.% of component Z6), and
• Z7) 0 to 10 wt.% of component Z7),

each based on the total weight of the cleaning compositions according to the invention.

The cleaning agent compositions according to the invention or the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention are advantageously suitable for the treatment of hard surfaces, preferably made of ceramic, stone, porcelain, glass, stainless steel, metal, plastic, linoleum or wood.

The present invention therefore further relates to the use of a cleaning agent composition according to the invention or of at least one copolymer of component Z1) of the cleaning agent compositions according to the invention for the treatment of hard surfaces, preferably made of ceramic, stone, porcelain, glass, stainless steel, metal, plastic, linoleum or wood. Preferably, the use according to the invention for the treatment of hard surfaces is carried out in order to achieve a cleaning effect on the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.

Furthermore, the use according to the invention for the treatment of hard surfaces is preferably carried out in order to impart hydrophilic properties to the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.

Furthermore, the use according to the invention for the treatment of hard surfaces is preferably carried out in order to produce shine on the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.

Furthermore, the use according to the invention for the treatment of hard surfaces is preferably carried out in order to improve the speed of drying of a hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.

Furthermore, the use according to the invention is preferably carried out for the treatment of hard surfaces in order to achieve permanent properties, preferably "anti-stain", "anti-trace" or "anti-streak", on the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.

Furthermore, the use according to the invention for the treatment of hard surfaces is preferably carried out in order to reduce the re-soiling of a hard surface to which the cleaning agent composition according to the invention or the at least one copolymer of component Z1) of the cleaning agent compositions according to the invention has been applied.

Furthermore, the use according to the invention for the treatment of hard surfaces is preferably carried out in order to facilitate the renewed cleaning of the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.

Furthermore, the use according to the invention is preferably carried out for the treatment of hard surfaces in order to achieve a repair effect of the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.

Furthermore, the use according to the invention is preferably carried out for the treatment of hard surfaces in order to remove grease residues or lime soap residues on the hard surface to which the cleaning agent composition according to the invention or the at least one copolymer of component Z1) of the cleaning agent compositions according to the invention has been applied.

Furthermore, the use according to the invention is preferably carried out for the treatment of hard surfaces in order to remove lime on the hard surface to which the cleaning agent composition according to the invention or the at least one copolymer of component Z1) of the cleaning agent compositions according to the invention has been applied, or to reduce new lime deposits.

Furthermore, the use according to the invention for the treatment of hard surfaces is preferably carried out in order to minimize or prevent the formation of a biofilm on the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.

Furthermore, the use according to the invention for the treatment of hard surfaces is preferably carried out in order to facilitate the rinsing of the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.

In a further preferred embodiment of the invention, the use according to the invention for treating hard surfaces is carried out in such a way that the cleaning agent composition according to the invention or the at least one copolymer of component Z1) of the cleaning agent compositions according to the invention remain on the hard surface after application ("leave-on" application).

In a further preferred embodiment of the invention, the use according to the invention for treating hard surfaces is carried out in such a way that the cleaning agent composition according to the invention or the at least one copolymer of component Z1) of the cleaning agent compositions according to the invention are removed from the hard surface after application and are preferably rinsed off with water ("rinse-off" application).

In a further preferred embodiment of the invention, the use according to the invention for treating hard surfaces is carried out for cleaning hard surfaces in the bathroom, hard surfaces in the kitchen, floors or toilets.

The present invention also further relates to a method for treating or cleaning a hard surface, characterized in that the hard surface is brought into contact with a cleaning agent composition according to the invention or with at least one copolymer of component Z1) of the cleaning agent compositions according to the invention.

The preferred embodiments given above for the cleaning agent compositions according to the invention also apply in a corresponding manner to the inventive use of the cleaning agent compositions according to the invention or of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention for treating hard surfaces and for the inventive method for treating or cleaning a hard surface using a cleaning agent composition according to the invention or at least one copolymer of component Z1) of the cleaning agent compositions according to the invention.

The invention is explained in more detail below by means of examples without being limited thereto. Unless explicitly stated otherwise in the examples, the percentages in the examples are to be understood as weight percent (wt.%).

Examples

The following abbreviations are used: AAPTAC [3-(Acryloylamino)-propyl]-trimethylammonium chloride (75 wt.% active in aqueous solution) AMPS-Na-Salt 2-Acryloylamino-2-methylpropanesulfonic acid, Na salt (50 wt.% active in aqueous solution) DADMAC Diallyldimethylammonium chloride (65 wt.% active in aqueous solution) DMAA N,N-Dimethylacrylamide (100% active) MAPTAC [3-(Methacryloylamino)-propyl]-trimethylammonium chloride (50 wt.% active in aqueous solution) MESNA 2-Mercaptoethanesulfonate sodium (100% active) Meth 1000 Polyethylene glycol-co-polypropylene glycol methacrylate, 1000 g/mol, 4-5 propylene glycol units (70 wt.% active in aqueous solution) Meth 5000 Polyethylene glycol-co-polypropylene glycol methacrylate, 5000 g/mol, 4-5 propylene glycol units (50 wt.% active in aqueous solution) MS-Na-Salt Maleic acid, sodium salt (100% active) NIPAM N-Isopropylacrylamide (100% active) NVP N-Vinylpyrrolidone (100% active) VA-44 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (100% active) V-PEG 1100 Polyethylene glycol vinyloxybutyl ether, 1100 g/mol (100% active) V-PEG 5000 Polyethylene glycol vinyloxybutyl ether, 5000 g/mol (100% active)

Production of copolymers General procedure for the preparation of copolymers

In a multi-neck flask equipped with a KPG stirrer, reflux condenser and N ₂ connection, the indicated amounts of chemicals (excluding the initiator) are dissolved in the indicated amount of distilled water under nitrogen (5 liters/hour) for the examples given in Table 1 for the preparation of copolymers of component Z1). It should be noted that some of the substances used to prepare the copolymers of component Z1) are used in aqueous form (see the information on the substances used to prepare the copolymers of component Z1). The distilled water indicated in Table 1 is added in addition to the water introduced via these substances. In the case of acidic monomers, these are pre-neutralized with a base such as an alkali carbonate, for example potassium carbonate. The aqueous solution is then flushed with nitrogen for 30 minutes and heated to 60 °C if VA-44 is used as the initiator, or to 80 °C if Na ₂ S ₂ O ₈ is used as the initiator. In the next step, the amount of initiator (VA-44 or Na ₂ S ₂ O ₈ ) specified in Table 1 is dissolved in 10 g of distilled water and metered in over a period of 90 minutes. After dosing is complete, stirring is continued for a further hour at an internal temperature of 60 °C if VA-44 is used as the initiator, or at an internal temperature of 80 °C if Na ₂ S ₂ O ₈ is used as the initiator. The conversion of the reaction is checked by a subsequent analysis of the solid and any unreacted monomers are reacted by adding a small amount of a 10 wt. % aqueous solution of the previously used initiator until complete conversion is achieved. The reaction mixture is then cooled to room temperature (20 - 23 °C).

Table 1 lists synthesis examples for copolymers of component Z1) of the cleaning compositions according to the invention. Table 1: Substances used to prepare the copolymers Copolymer No. V-PEG 1100 V-PEG 5000 Meth 1000 Meth 5000 AAPTAC NIPAM DMAA DADMAC MAPTAC NVP AMPS-Na-Salt MS-Na-Salt Na-hypophosphite MESNA VA-44 _{Na2S2O8 ​ ​} dest. _H2O [g] M _f [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [G] [G] [G] [G] [g/mol] 1 - 4,816 - - 32,985 80,064 - - - - - - 0.120 - 1,560 - 149,450 39284 2 - 4,816 - - 32,985 - 91,395 - - - - - 0.120 - 1,560 - 149,450 36396 3 - 4,816 - - - - 22,899 - 61,294 - - - - - 1,560 - 136,000 42261 4 - 4,816 - - - - 22,899 83,755 - - - - - - 1,560 - 142,250 10934 5 - 4,816 - - - 20,060 - - 61,294 - - - - - 1,560 - 136,000 6 - 4,816 - - - - 57,198 - 46,163 - - - - - 1,560 - 139,500 102330 7 - 4,816 - - - 80,064 - - 30,760 - - - 0.120 - 1,560 - 144,860 35849 10 - 4,816 - - - 50,000 - - 46,000 - - - - - 1,560 - 697,500 91934 11 - 4,816 - - - 80,064 - - 30,760 - - - - - 1,560 - 724,300 12 29,809 - - - - 14,758 - - 25,777 - - - 0.120 - 1,560 - 80,000 13 29,809 - - - - 14,758 - - 25,777 - - - - - 1,560 - 149,500 14 - - - 8,750 30,328 55,232 - - - 56,235 - - - 0.180 1,560 - 131,670 15 - - 34,370 - 30,328 55,232 - - - 140,543 - - - 0.540 1,560 - 160,700 16 - - 49,994 - 27,670 14,758 - - - - - - - 0.180 1,560 - 138,780 17 - - - 10,000 28,034 - - - - - 9,989 - - 0.180 1,560 - 105,000 18 - - - 6,794 27,670 14,758 - - - - - - 0.180 - 1,150 162,790 19 - 4,816 - - - - 91,395 - 30,760 - - - 0.120 - 1,560 - 149,450 20 - 4,816 - - - - 91,395 - 30,760 - - 1,090 - - 1,560 - 149,450

The amounts given in Table 1 are based on the active ingredient Table 1a: Relative amounts according to Table 1 Copolymer No. Total amount of monomers used [mmol] Structural units (A) [mol-%] Structural units (B) [mol-%] Structural units (C) [mol-%] Structural units (D) [mol-%] 1 117,865 28.0 4.1 67.9 - 2 129,196 25.5 3.7 70.7 - 3 89,009 68.9 5.4 25.7 - 4 111,470 75.1 4.3 20.5 - 5 86,170 71.1 5.6 23.3 - 6 108,177 42.7 4.5 52.9 - 7 115,640 26.6 4.2 69.2 - 10 100,816 45.6 4.8 49.6 - 11 115,640 26.6 4.2 69.2 - 12 70,344 36.6 42.4 21.0 - 13 70,344 36.6 42.4 21.0 - 14 150,545 20.1 5.8 74.0 - 15 260,473 11.6 13.2 75.2 - 16 92,422 29.9 54.1 16.0 - 17 48,023 58.4 20.8 20.8 - 18 49,222 56.2 13.8 30.0 - 19 126,971 24.2 3.8 72.0 - 20 128,061 24.0 3.8 71.4 0.9

Determination of weight average molecular weights M _w by GPC:

Method description:

Pillar: PSS NOVEMA MAX Guard, 1x30Å & 2x1000Ä 10 µm, 300 mm x 8 mm Detector: RI Oven temperature: 25°C Flow: 1 ml / minute Injection volume: 50 µl Eluent: 79.7 vol% 0.1M NaCl + 0.3 vol% TFA (trifluoroacetic acid) + 20.0 vol% ACN (acetonitrile) Calibration method: conventional calibration Standards: Poly(2-vinylpyridine) in the range of 1110 to 1 060 000 Dalton

Measured weight-average molecular weights for copolymers of component Z1) of the cleaning compositions according to the invention are given in Table 1.

Shining power

Black, glossy ceramic tiles (10 × 10 cm) are pre-cleaned and then about 10 drops of the cleaning agent composition are applied to the center of the tiles. The cleaning agent composition is evenly distributed on the tile using a folded cellulose kitchen towel. After the tiles have dried vertically for at least 30 minutes, a visual assessment (grade 1 - 10) of the tiles is carried out, with 1 being considered the best and 10 the worst grade.

Example formulations with and without copolymer of component Z1) of the cleaning compositions according to the invention were prepared and Gloss tests were conducted with these formulations. The example formulations and gloss results are shown in Table 2. Table 2 Example formulations and gloss results Cleaning agent composition A B C D E F G H C11 alcohol ethoxylate [wt.%] 4.0 2.5 4.5 4.0 2.5 4.5 1.0 - Propylene glycol butyl ether [wt.%] 1.0 0.6 0.5 1.0 0.6 0.5 - - Alkylpolyglucoside [wt.%] - 1.0 - - 1.0 - - - Sodium alkylbenzenesulfonate [wt.%] - - - - - - 2.0 0.5 Lactic acid [wt.%] - - - - - - 1.5 - Dipropylene glycol monobutyl ether [wt.%] - - - - - - - 0.25 Ammonium hydroxide [wt.%] - - - - - - - 0.3 Benzalkonium chloride [wt.%] - 0.4 - - 0.4 - - - Isopropanol [wt.%] - - - - - - - 7.0 Water [wt.%] to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 pH (adjusted with NaOH or citric acid) 7 7 7 10 10 10 3.4 11.3 Visual assessment Without additive 6.3 2.5 10.0 9.2 3.0 10.0 10.0 7.0 + 0.2 wt.% copolymer 1 2.0 2.0 2.0 1.7 2.0 2.0 - - + 0.2 wt.% copolymer 2 2.0 - - 2.7 - - - - + 0.2 wt.% copolymer 3 3.0 - - 3.0 - - - - + 0.2 wt.% copolymer 4 3.3 - - 2.3 - - - 1.3 + 0.2 wt.% copolymer 5 2.0 - - 2.7 - - - - + 0.2 wt.% opolymer 6 - - - - - - 3.7 2.0

The results in Table 2 show that by using the copolymers of component Z1) in the example formulations, better gloss results can be achieved compared to the corresponding example formulations without copolymer of component Z1).

Cleaning agent compositions were prepared analogously using copolymers 7 and 10-20.

Market cleaners were mixed with copolymers of component Z1) of the cleaning agent compositions according to the invention and gloss tests were carried out with the market cleaners with and without copolymer. The results are shown in Table 3. Table 3 Use of copolymers in market cleaners cleanser Market Cleaner 1 Spray All-Purpose Cleaner Market Cleaner 2 Spray Bathroom Cleaner Market Cleaner 3 Spray Cleaner pH 11 2.9 2.5 Without additive 10 6.3 5.3 + 0.2 wt.% copolymer 6 2.0 1.0 1.0 + 0.2 wt.% copolymer 4 2.0 1.0 2.7

Table 3 shows that by using the copolymers of component Z1) of the cleaning agent compositions according to the invention in commercial cleaners, better shine results can be achieved compared to the corresponding commercial cleaners without the addition of a copolymer of component Z1).

Adsorption tests on hard surfaces

The tests were carried out using the quartz crystal microbalance QCM-D (Quartz Crystal Microbalance with Dissipation Monitoring, Q-Sense, Västra Frölinda, Sweden). The method is based on the change in the natural frequency of a piezoelectric quartz crystal as soon as it is loaded with a mass. The surface of the quartz can be modified by spin coating or vapor deposition. The quartz oscillator is located in a measuring cell. The measuring cell is a flow cell into which the solution to be examined is pumped from storage vessels. The pump speed is kept constant during the measurement. Typical pump speeds are between 50-250 µl/minute. During a measurement, it is important to ensure that the tubes and measuring cell are free of air bubbles. Each measurement begins with the recording of the baseline, with respect to which all frequency and dissipation measurements are set as the zero point. In this example, commercially available quartz crystals with a 50 nm thick silicon dioxide coating (QSX303, Q-Sense, Västra Frölinda, Sweden) and quartz crystals with a 50 nm thick stainless steel (SS2343) coating (QSX304 Q-Sense, Västra Frölinda, Sweden) were used.

Aqueous solutions of the copolymers of component Z1) of the cleaning compositions according to the invention with an active content of 2000 ppm were investigated. Tap water with 20° dH was used as the water. The pH was adjusted to pH 10 with NaOH or citric acid. Table 4 Adsorption of copolymers on silica: Copolymer No. Adsorbed mass [ng/cm ² ] 5 264.4 3 275.9 6 355.8 4 142.5 7 348.0 19 102.7 20 330.4 Copolymer No. Adsorbed mass [ng/cm ² ] 5 129.7 3 153.6 19 121.0 20 156.6

The results of Tables 4 and 5 show that the copolymers of component Z1) of the cleaning compositions according to the invention are suitable for use on hard surfaces since they adsorb on the inorganic surfaces investigated.

Contact angle test

The contact angles were measured on various surfaces (ceramic, glass, stainless steel) by modifying the surfaces using the following method: The surfaces were dipped three times for 2 minutes in fresh demineralized water (deionized water) and then dipped in the respective aqueous copolymer solution for 20 minutes at room temperature while stirring to modify them. The surfaces were then dried with a gentle stream of nitrogen. The contact angle was measured on the surfaces prepared in this way using deionized water (apparatus: drop analyzer from Krüss, Hamburg, model DSA 100).

The height of the contact angle of a water drop on a surface is a measure of its hydrophilization. A very hydrophilic surface is completely wetted by a water drop. This phenomenon is also called spreading of the drop.

Copolymers of component Z1) of the cleaning compositions according to the invention were investigated as an aqueous solution with an active content of 2000 ppm. Tap water with 20° dH was used as the water. The pH value was adjusted to pH 10 with NaOH or citric acid. Table 6 Contact angle on black ceramic tile Copolymer No. Contact angle of water Untreated 18° 5 8° 3 Drop spreads 6 4.2° 4 15° 7 5° 19 Drop spreads 20 Drop spreads Copolymer No. Contact angle of water Untreated 39° 6 Drop spreads 4 Drop spreads 7 Drop spreads Copolymer No. Contact angle of water untreated 15° 5 Drop spreads 3 Drop spreads 19 8° 20 13°

The results of Tables 6, 7 and 8 show that the copolymers of component Z1) of the cleaning compositions according to the invention are suitable for reducing the contact angle of water on inorganic surfaces (ie for hydrophilizing inorganic surfaces).

Repair effect

The topography of the surface of a damaged black tile was determined before and after treatment with aqueous solutions of the copolymers of component Z1) of the cleaning agent compositions according to the invention with an active content of 2000 ppm (equipment: contact-free optical 3D surface characterization from Sensofar, Barcelona, Model S neox). Using the MountainsMap software (Digital Surf SARL, Besancon, France), various 3D parameters can be calculated by segmenting the topography of a surface into surface elements. These parameters provide information on height information (calculation according to ISO 25178) and roughness (calculation according to ISO 4287). Table 9 Roughness of a black damaged tile before and after copolymer treatment Copolymer No. Roughness untreated [nm] Roughness after treatment [nm] 3 71* 36* 6 140 94.6 4 110 108 7 86 85 * Changing the roughness of a black tile

The investigations clearly demonstrate the repair effect of the copolymers of component Z1) of the cleaning compositions according to the invention.

Claims (25)

1. Detergent composition comprising

   Z1) one or more copolymers containing

   a) 0.1 to 99.8 mol%, preferably 25.0 to 80.0 mol% and more preferably 25.0 to 77.6 mol% of one or more cationic structural units (A)

   b) 0.1 to 99.8 mol%, preferably 0.4 to 4.5 mol% and more preferably 0.5 to 4.4 mol% of one or more macromonomeric structural units (B) and

   c) 0.1 to 99.8 mol% of one or more structural units (C) which differ from the structural units (A) and (B),

   characterized in that the one or more cationic structural units (A) are represented by the following general formulae (I) and/or (II):

   

   

   in which

   R¹ and R^1a are each the same or different and are each independently hydrogen and/or a methyl radical,

   R^1b, R³, R⁴ and R⁵ are each the same or different and are each independently represented by hydrogen, an aliphatic hydrocarbyl radical having 1 to 20 and preferably 1 to 4 carbon atoms, a cycloaliphatic hydrocarbyl radical having 5 to 20 and preferably 5 to 8 carbon atoms, an aryl radical having 6 to 14 carbon atoms and/or polyethylene glycol (PEG), are preferably each the same or different and each independently represented by hydrogen and/or methyl and are more preferably each methyl,

   Y is the same or different and is represented by oxygen, NH and/or NR³,

   V is the same or different and is represented by -(CH₂)_x-,

   

   x , is the same or different and is represented by an integer from 1 to 6,

   X and X₁ are each the same or different and are each independently represented by a halogen atom, C₁- to C₄-alkylsulfate and/or C₁- to C₄-alkylsulfonate,

   and the one or more macromonomeric structural units (B) are represented by the general formula (III):

   

   in which

   R^x is the same or different and is represented by H and/or methyl,

   Z is the same or different and is represented by C=O and/or O(CH₂)₄ and is preferably O(CH₂)₄,

   1 on molar average is a number from 0 to 7 and preferably from 0 to 6, and

   p on molar average is a number from 1 to 150, preferably from 11 to 150 and more preferably from 12 to 150,

   and the one or more structural units (C) are the polymerization product of at least one monomer species selected from the group consisting of noncationic acrylamides, noncationic methacrylamides and N-vinyl-substituted lactams having 5 to 7 ring atoms,
   and

   Z2) one or more surfactants
   and

   Z3) water,
   where the detergent composition contains the one or more copolymers of component Z1) in an amount of 0.005% to 10% by weight, based on the total weight of the detergent composition.
2. Detergent composition according to Claim 1, characterized in that the one or more cationic structural units (A) of the one or more copolymers of component Z1) are the polymerization product of at least one monomer species selected from the group consisting of [2-(acryloyloxy)ethyl]trimethylammonium chloride, [2-(acryloylamino)ethyl]trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium methosulfate, [2-(methacryloyloxy)ethyl]trimethylammonium chloride or methosulfate, [3-(acryloylamino)propyl] trimethylammonium chloride, [3-(methacryloylamino)propyl]trimethylammonium chloride and diallyldimethylammonium chloride (DADMAC), preferably selected from the group consisting of [3-(acryloylamino)propyl]trimethylammonium chloride, [3-(methacryloylamino)propyl]trimethylammonium chloride and diallyldimethylammonium chloride, and more preferably selected from the group consisting of [3-(methacryloylamino)propyl]trimethylammonium chloride and diallyldimethylammonium chloride.
3. Detergent composition according to Claim 1 or 2, characterized in that the one or more macromonomeric structural units (B) of the formula (III) of the one or more copolymers of component Z1) are the polymerization product of at least one monomer species selected from the group consisting of polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether (in which 1 on molar average is a number from 1 to 7, preferably from 2 to 6 and more preferably from 3 to 6), polyethylene glycol (meth)acrylate and polyethylene glycol-co-polypropylene glycol (meth)acrylate (in which 1 on molar average is a number from 1 to 7, preferably from 2 to 6 and more preferably from 3 to 6).
4. Detergent composition according to one or more of Claims 1 to 3, characterized in that, in the one or more macromonomeric structural units (B) of the formula (III) of the one or more copolymers of component Z1),

   i) R^x is H, 1 = 0 and p on molar average is a number from 1 to 150, preferably from 11 to 150 and more preferably from 12 to 150 when Z is O(CH₂)₄ or

   ii) R^x is the same or different and is represented by H and/or methyl, 1 on molar average is a number from 1 to 7, preferably from 2 to 6 and more preferably from 3 to 6, and p on molar average is a number from 1 to 150, preferably from 11 to 150 and more preferably from 12 to 150 when Z is C=O.
5. Detergent composition according to one or more of Claims 1 to 4, characterized in that the one or more copolymers of component Z1) contain 25.0 to 80.0 mol% of the one or more structural units (A), 0.4 to 4.5 mol% of the one or more structural units (B) and 15.5 to 74.6 mol% of the one or more structural units (C).
6. Detergent composition according to one or more of Claims 1 to 5, characterized in that the one or more copolymers of component Z1) contain 25.0 to 77.6 mol% of the one or more structural units (A), 0.5 to 4.4 mol% of the one or more structural units (B) and 18.0 to 74.5 mol% of the one or more structural units (C).
7. Detergent composition according to one or more of Claims 1 to 6, characterized in that the one or more structural units (C) of the one or more copolymers of component Z1) are selected from the group consisting of the polymerization product of at least one N-vinyl-substituted lactam having 5 to 7 ring atoms and the structural units of the following general formulae (IV) and/or (V):

   

   in which

   R¹ is the same or different and is hydrogen and/or methyl, and

   R³ and R⁴ are each the same or different and are each independently represented by hydrogen, an aliphatic hydrocarbyl radical having 1 to 20 and preferably 1 to 4 carbon atoms, a cycloaliphatic hydrocarbyl radical having 5 to 20 and preferably 5 to 8 carbon atoms, an aryl radical having 6 to 14 carbon atoms, an alkylaryl radical having 7 to 14 carbon atoms, a branched or unbranched C₁-C₅-monohydroxyalkyl group and/or polyethylene glycol (PEG),

   

   in which

   R¹¹ is the same or different and is represented by H and/or methyl;

   X is the same or different and is represented by NH-(C_nH_2n) with n = 1, 2, 3 or 4; and

   R¹³ is the same or different and is represented by OH, N(CH₃)₂, SO₃H, PO₃H₂, O-PO₃H₂ and/or para-substituted C₆H₄-SO₃H.
8. Detergent composition according to Claim 7, characterized in that the one or more structural units (C) of the one or more copolymers of component Z1) are selected from the structural units of the general formula (IV) .
9. Detergent composition according to one or more of Claims 1 to 8, characterized in that the one or more structural units (C) of the one or more copolymers of component Z1) are the polymerization product of at least one monomer species selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-cyclohexyl-acrylamide, N-benzylacrylamide, N-methylolacrylamide, N-isopropylacrylamide and N-tert-butylacrylamide and preferably selected from the group consisting of N,N-dimethylacrylamide and N-isopropylacrylamide.
10. Detergent composition according to one or more of Claims 1 to 9, characterized in that the one or more copolymers of component Z1), in addition to the structural units (A), (B) and (C), contain one or more structural units (D) which differ from the structural units (A), (B) and (C), and where the one or more copolymers contain

    preferably 0.1 to 99.7 mol% of the one or more structural units (A), 0.1 to 99.7 mol% of the one or more structural units (B), 0.1 to 99.7 mol% of the one or more structural units (C) and 0.1 to 99.7 mol% of the one or more structural units (D),

    more preferably 25.0 to 80.0 mol% of the one or more structural units (A), 0.4 to 4.5 mol% of the one or more structural units (B), 15.5 to 60.0 mol% of the one or more structural units (C) and 0.1 to 14.6 mol% of the one or more structural units (D), and

    especially preferably 25.0 to 77.6 mol% of the one or more structural units (A), 0.5 to 4.4 mol% of the one or more structural units (B), 18.0 to 50.0 mol% of the one or more structural units (C) and 0.5 to 24.6 mol% of the one or more structural units (D).
11. Detergent composition according to Claim 10, characterized in that the one or more copolymers of component Z1) contain one or more structural units (D) selected from the structural units of the following general formulae (IX) and/or (X):

    

    in which

    R¹¹ is the same or different and is represented by H and/or methyl;

    Z is the same or different and is represented by O and/or NH;

    

    in which

    R¹¹ is the same or different and is represented by H and/or methyl;

    Q is the same or different and is represented by O and/or NH; and

    R¹⁵ is the same or different and is represented by H, (C_nH_2n)-SO₃H with n = 0, 1, 2, 3 or 4; (C_nH_2n)-OH with n = 0, 1, 2, 3 or 4; (C_nH_2n)-PO₃H₂ with n = 0, 1, 2, 3 or 4; (C_nH_2n)-OPO₃H₂ with n = 0, 1, 2, 3 or 4; (C₆H₄)-SO₃H; (C₆H₄)-PO₃H₂; (C₆H₄)-OPO₃H₂ and/or (C_mH_2m)_e-O-(A'O)_u-R¹⁶ with m = 0, 1, 2, 3 or 4, e = 0, 1, 2, 3 or 4, A' = C_x'H_2x' with x' = 2, 3, 4 or 5, u = an integer from 1 to 350 and R¹⁶ is the same or different and is represented by an unbranched or branched C₁-C₄-alkyl group.
12. Detergent composition according to one or more of Claims 1 to 11, characterized in that the structural units (A), (B), (C) and optionally (D) of the one or more copolymers of component Z1) are present in the copolymer in a random, blockwise, alternating or gradient distribution.
13. Detergent composition according to one or more of Claims 1 to 12, characterized in that the weight average molecular weight M_w of the one or more copolymers of component Z1) is from 10 000 to 250 000 g/mol, preferably from 15 000 to 200 000 g/mol and more preferably from 20 000 to 150 000 g/mol.
14. Detergent composition according to one or more of Claims 1 to 13, characterized in that it comprises the one or more copolymers of component Z1) in an amount of 0.01% to 5% by weight and preferably in an amount of 0.1% to 0.5% by weight, based in each case on the total weight of the detergent composition.
15. Detergent composition according to one or more of Claims 1 to 14, characterized in that the one or more surfactants of component Z2) are selected from the group consisting of anionic, nonionic, amphoteric and cationic surfactants.
16. Detergent composition according to Claim 15, characterized in that the one or more surfactants of component Z2) are selected from the group consisting of fatty alcohol polyglycol ethers, alkyl polyglycosides, alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfates, alkyl sulfates and quaternary ammonium compounds.
17. Detergent composition according to one or more of Claims 1 to 16, characterized in that the proportion of the one or more surfactants of component Z2) in the detergent composition of the invention is from 0.1% to 20% by weight and preferably from 0.1% to 6.0% by weight, based in each case on the total weight of the detergent composition.
18. Detergent composition according to one or more of Claims 1 to 17, characterized in that it comprises, in addition to the one or more copolymers of component Z1), the one or more surfactants of component Z2) and water of component Z3), one or more further substances selected from components Z4), Z5), Z6) and/or Z7):

    Z4) one or more inorganic or organic acids as component Z4),

    Z5) one or more complexing agents as component Z5),

    Z6) one or more solvents other than water as component Z6),

    Z7) one or more further additives, preferably selected from the group consisting of viscosity regulators, enzymes, bleaches, preservatives, fragrances and dyes, as component Z7),

    and the pH of the detergent composition is preferably from 1 to 14 and more preferably from 3 to 11.
19. Detergent composition according to Claim 18, characterized in that it comprises

    Z1) 0.005% to 10.00% by weight of component Z1),

    Z2) 0.10% to 20.00% by weight of component Z2),

    Z3) 10.00% to 99.8% by weight of component Z3),

    Z4) 0% to 10% by weight of component Z4),

    Z5) 0% to 10% by weight of component Z5),

    Z6) 0% to 10% by weight of component Z6), and

    Z7) 0% to 10% by weight of component Z7),

    based in each case on the total weight of the detergent composition.
20. Use of a detergent composition according to one or more of Claims 1 to 19 or of at least one copolymer as defined in one or more of Claims 1 to 13 for treatment of hard surfaces, preferably of ceramic, stone, porcelain, glass, stainless steel, metal, plastic, linoleum or wood.
21. Use according to Claim 20 for imparting hydrophilic properties to the hard surface on which the detergent composition or the at least one copolymer has been employed.
22. Use according to Claim 20 for producing shine on the hard surface on which the detergent composition or the at least one copolymer has been employed.
23. Use according to Claim 20 for achieving permanent properties, preferably "anti-stain", "anti-trace" or "anti-streak" properties, on the hard surface on which the detergent composition or the at least one copolymer has been applied.
24. Use according to Claim 20 for achieving a repair effect on the hard surface on which the detergent composition or the at least one copolymer has been employed.
25. Method of treating or cleaning a hard surface, characterized in that the hard surface is contacted with a detergent composition according to one or more of Claims 1 to 19 or with at least one copolymer as defined in one or more of Claims 1 to 13.