EP3127995A1 - Novel, whiteness reinforcing detergent - Google Patents

Abstract

The present invention relates to a washing, cleaning or pretreatment agent for textiles. Surprisingly, it has been found that, through the use of certain fatty acid esters in conjunction with at least one surfactant, an improved whiteness and / or lightness (whiteness) effect can be achieved.

Description

The present invention relates to a washing, cleaning or pretreatment agent for, inter alia, textiles. Surprisingly, it has been found that by using certain fatty acid oligoesters in combination with at least one surfactant, an improved whitening and / or whitening effect can be achieved. Thus, fatty acid oligoesters act as so-called whitening and / or whiteness enhancers.

To clean heavily soiled laundry, high temperatures of 60 ° C or more are often required. While such temperatures are possible for the cleaning of bed or table linen or similar durable materials, garments in particular are often made of such materials that can only be washed at a temperature of about 30 ° C or 40 ° C. This applies in particular to so-called "easy-care" textiles and garments, which are often referred to as, for example, "easy-care", "non-iron", etc., and are marketed and increase in importance in the market. The realization of such properties dictates that Easy-Care products are mostly made from synthetic fibers and thus can only be washed at low temperatures such as 30 ° C or 40 ° C.

Such low cleaning temperatures are also increasingly finding the approval of consumers. In order to allow the most environmentally friendly cleaning, garments are washed at ever lower temperatures. This creates a power savings. From the manufacturer's point of view, the setting for washing programs is often chosen so that a lower temperature prevails during the wash cycle with a view to environmentally friendly cleaning of clothing. In addition, water consumption is significantly lower in modern machines than in older models.

Despite reduced temperature and despite water savings, a thorough cleaning must still be achieved even under the changed washing conditions. In addition, with regard to the cleaning of textiles, consumer expectations have even increased. Even white textiles should not gray or yellow after several washes, colored textiles should retain their color and the fabric should be spared; At the same time, all types of soiling are to be removed even at low temperatures.

With regard to a more environmentally friendly washing, consumers are increasingly paying attention to the composition of the detergents. These should have as few polluting components as possible.

In addition, liquid detergents are becoming increasingly important in commerce. In contrast to solid detergents, liquid detergents have no bleaching systems, since they can not be integrated here in a storage-stable manner. In particular, in the removal of those stains which can be usually removed by bleaching (bleach-sensitive stains), the detergency of liquid detergents can not always keep up with that of solid detergents.

Frequently, optical brighteners are also added to the detergent in order to make the laundry (in particular light-colored or white laundry) appear optically brighter. This is particularly the case with liquid detergents with reduced cleaning performance compared to bleach-sensitive stains, the use of which discolors textiles after a few washes. Optical brighteners may in particular be added to the detergents in order to optically level graying and yellowing of the treated textiles on the fiber. These substances are absorbed by the fiber and cause brightening and fake bleaching by converting invisible ultraviolet radiation to visible longer wavelength light, with the ultraviolet light absorbed from sunlight being emitted as faint bluish fluorescence and the yellowness of the bated or yellowed Laundry pure white results. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives.

There is therefore a need for detergents, in particular for liquid detergents, which, despite a potentially lower content of optical brighteners compared to the prior art, allow textiles to continue to be light or white even after several washes. Furthermore, white textiles should be preserved even with more frequent washes on white textiles, and no graying or yellowing should occur. Ideally, and in contrast to the underlying mechanism of optical brighteners, these effects are to be realized by an increased degree of cleanliness of the respective textiles. Surprisingly, it has been shown that the use of certain fatty acid oligoesters washing, cleaning or pretreatment can be provided which lead to an improved whiteness of the washed textiles.

1. 1) wenigstens einen Fettsäureoligoester der Formel (I)
   
   worin
   • KW für ein lineares oder verzweigtes, gesättigtes oder ungesättigtes Kohlenwasserstoffgerüst mit einer Anzahl z an Kohlenstoffatomen von 3, 4, 5, 6, 7 oder 8 steht, und wobei jedes Kohlenstoffatom des Kohlenwasserstoffgerüsts an nicht mehr als ein Sauerstoffatom direkt gebunden ist,
   • EO für einen Ethylenoxy-Rest abgeleitet von Ethylenoxid steht,
   • PO für einen Propylenoxy-Rest abgeleitet von Propylenoxid steht,
   • für jeden Rest unabhängig k und h die Anzahl der in besagtem Rest enthaltenen Reste EO und PO bedeuten und unabhängig voneinander für eine Zahl von 1 bis 500, insbesondere von 1 bis 250, stehen,
   • für jeden Rest unabhängig a und b die Anzahl der in besagtem Rest enthaltenen Reste EO und PO bedeuten und unabhängig voneinander für 0 oder eine Zahl von 1 bis 500, insbesondere von 1 bis 250, stehen,
   • R für einen geradkettigen oder verzweigten, gesättigten oder ungesättigten C₄-C₄₉-Kohlenwasserstoffrest steht,
   • t für eine ganze Zahl von 3 bis z steht,
   • s für eine ganze Zahl von 0 bis (z-3) steht,
   mit der Maßgabe, dass die Summe aus s + t für eine ganze Zahl von 3 bis z steht, und
   mit der weiteren Maßgabe, dass nicht mehr als 4 Kohlenstoffatome zwischen zwei direkt mit KW gebundenen Sauerstoffatomen vorliegen,
   und
2. 2) mindestens ein Tensid, das kein Fettsäureoligoester gemäß 1) ist.

In a first embodiment, the object underlying the present invention is therefore achieved by containing a washing, cleaning or pretreatment agent

1. 1) at least one fatty acid oligoester of the formula (I)
   
   wherein
   • KW is a linear or branched, saturated or unsaturated hydrocarbon backbone having a number z of carbon atoms of 3, 4, 5, 6, 7 or 8, and wherein each carbon atom of the hydrocarbon backbone is directly attached to not more than one oxygen atom,
   • EO is an ethyleneoxy radical derived from ethylene oxide,
   • PO is a propyleneoxy radical derived from propylene oxide,
   • independently of one another k and h denote the number of radicals EO and PO contained in the said radical and independently of one another represent a number from 1 to 500, in particular from 1 to 250,
   • independently of one another, a and b denote the number of radicals EO and PO contained in said radical and represent, independently of one another, 0 or a number from 1 to 500, in particular from 1 to 250,
   • R is a straight-chain or branched, saturated or unsaturated C ₄ -C ₄₉ -hydrocarbon radical,
   • t is an integer from 3 to z,
   • s is an integer from 0 to (z-3),
   with the proviso that the sum of s + t stands for an integer from 3 to z, and
   with the further proviso that there are not more than 4 carbon atoms between two oxygen atoms directly bonded with HC,
   and
2. 2) at least one surfactant which is not a fatty acid oligoester according to 1).

Among the units

sind Ketten zu verstehen, die aus einer beliebigen Mischung von EO- und PO-Einheiten bestehen. Diese können, wie dargestellt, eine Reihe von EO-Einheiten gefolgt von einer Reihe von PO-Einheiten aufweisen. Alternativ können die Ketten auch eine Reihe von beispielsweise EO-Einheiten gefolgt von einer Reihe von PO-Einheiten und dann wieder eine Reihe von EO-Einheiten aufweisen. Sind k und h bzw. a und b nicht null, liegt ein Copolymer vor. Dieses kann als Block-Copolymer oder als alternierendes Copolymer oder als statistisch verteiltes Copolymer vorliegen. In allen Fällen stehen jeweils k und a bzw. h und b für die gesamte Menge von EO- beziehungsweise PO-Einheiten der jeweiligen Kette ungeachtet deren Reihenfolge in der Kette.

are chains that consist of any mixture of EO and PO units. These can have a number of EO units followed by a number of PO units, as shown. Alternatively, the chains may also comprise a series of, for example, EO units followed by a series of PO units and then again a series of EO units. If k and h or a and b are not zero, a copolymer is present. This may be in the form of a block copolymer or an alternating copolymer or a random copolymer. In all cases, k and a and h and b, respectively, stand for the entire set of EO or PO units of the respective chain regardless of their order in the chain.

In a structural formula, bonds denoted by a * denote the free valence of an atom of an affected residue through which the said residue binds.

Surprisingly, with the washing, cleaning or pretreatment agent according to the invention, an improved lightening effect and / or increased whiteness on fabric compared with washing, cleaning or pretreatment agents which are free from the fatty acid oligoesters of the invention are achieved. In particular, with the formulation according to the invention, a clear improvement in the whiteness is obtained so that graying and / or yellowing, especially of white textiles, can be avoided.

The fatty acid esters of the present invention are known in the art and are commonly used as thickeners in shampoos, shower gels and bath foams. Neither their use in washing, cleaning or pretreatment agents nor their action as whitening / whitening enhancers is described in the prior art.

In contrast to washing, cleaning or pretreatment agents known in the prior art, the content of optical brighteners can be significantly reduced or even dispensed with. Despite this reduced level of optical brighteners used, it is possible to achieve outstanding whiteness. Furthermore, the low proportion / absence of optical brighteners allows an environmentally friendly cleaning that is not inferior to the cleaning performance of conventional solid or liquid detergents, but significantly exceeds the whiteness of detergents that do not receive the fatty acid oligoesters of the invention. The washing, cleaning or pretreatment agent according to the invention is preferably a liquid washing, cleaning or pretreatment agent. Preferably, the washing, cleaning or pretreatment agent according to the invention is free of bleach. Particularly preferred is a liquid bleach-free washing, cleaning or pretreatment agent.

Without wishing to be bound by the mechanism of action, the fatty acid oligoesters could bind dirt particles in the detergent liquor. Due to their favorable hydrophilic / hydrophobic structure is a collection of dirt particles on the laundry, as known for example in the polyacrylates prevented. Thus, or for some other reason, the fatty acid oligoesters have a direct positive influence on the lightening and / or whiteness of the laundry. Dirt particles can no longer easily be absorbed by the fleet onto the fabric, as a result of which graying or yellowing of the textiles is prevented or significantly reduced.

The composition according to the invention, ie the washing, cleaning or pretreatment agent, contains at least one fatty acid oligoester according to the above-described general formula (I).

KW represents a linear or branched, saturated or unsaturated hydrocarbon backbone having a number z of carbon atoms of 3, 4, 5, 6, 7 or 8, wherein each carbon atom of the hydrocarbon backbone is bonded to not more than one oxygen atom. KW therefore represents a C ₃ -C ₈ hydrocarbon skeleton (C ₃ -C ₈ skeleton), to which preferably at least 3 to 5 oxygen atoms are bonded directly. In one embodiment, 3 oxygen atoms are bonded directly to the backbone. In one embodiment, 4 oxygen atoms are bonded directly to the backbone. In one embodiment, 5 oxygen atoms are bonded directly to the backbone. Also, more than 5, such as 6, oxygen atoms may be directly attached to the backbone.

In one embodiment, HC represents a C ₄ backbone to which 4 oxygen atoms are directly attached. In one embodiment, KW represents a C ₅ backbone to which 3 oxygen atoms are directly attached. In one embodiment, KW represents a C ₅ backbone to which 4 oxygen atoms are directly attached. In one embodiment, KW represents a C ₅ backbone to which 5 oxygen atoms are directly attached. In one embodiment, KW represents a C ₆ skeleton to which 4 oxygen atoms are directly attached. In one embodiment, KW represents a C ₆ backbone to which 5 oxygen atoms are directly attached. In one embodiment, KW represents a C ₆ skeleton to which 6 oxygen atoms are directly attached. In one embodiment, HC represents a C ₇ backbone to which 3 oxygen atoms are directly attached. In one embodiment, HC represents a C ₇ backbone to which 4 oxygen atoms are directly attached. In one embodiment, KW represents a C ₇ backbone to which 5 oxygen atoms are directly attached. In one embodiment, KW represents a C ₇ backbone to which 6 oxygen atoms are directly attached.
In one embodiment, KW represents a C ₈ skeleton to which 3 oxygen atoms are directly attached. In one embodiment, HC represents a C ₈ backbone to which 4 oxygen atoms are directly attached. In one embodiment, HC represents a C ₈ backbone to which 5 oxygen atoms are directly attached. In one embodiment, HC represents a C ₈ backbone to which 6 oxygen atoms are directly attached. In a preferred embodiment, KW a C ₄ skeleton to which 3 oxygen atoms are directly attached. In a further preferred embodiment, KW represents a C ₃ skeleton to which 3 oxygen atoms are directly bonded. In a particularly preferred embodiment, KW represents a C ₆ skeleton, to which 3 oxygen atoms are directly bonded.

In the formula (I), t is an integer of 3 to z and s is an integer of 0 to (z-3). Therefore, s can stand for 0, 1, 2, 3, 4 or 5. In a preferred embodiment, z is 4 and s is 1, preferably 2. In a preferred embodiment, z is 6, s is 0, and t is 3.

In formula (I), R represents a C ₄ -C ₄₉ , preferably a C ₄ -C ₂₉ , or a C ₇ -C ₁₉ straight-chain or branched, saturated or unsaturated hydrocarbon radical. R is derived from a corresponding fatty acid, ie R represents the hydrocarbon chain of a corresponding fatty acid (ie for the fatty acid without CO ₂ H group). For example, if R is a straight-chain, saturated C ₄ hydrocarbon radical, it means that R is derived from n-pentanoic acid. Suitable saturated and unsaturated fatty acids from which R can be derived are, for example, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, Lignoceric acid, cerotic acid, montanic acid, melissic acid, lacceric acid, geddic acid, undecylenic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, icosenoic acid, cetoleic acid, erucic acid, nervonic acid, and linoleic acid. Particularly preferred are C ₈ -C ₂₀ fatty acids and natural fatty acid mixtures, for example, the fatty acid mixtures contained in palm, coconut, palm kernel, and olive oil and tallow fatty acid. These fatty acid esters may be present in unmodified or modified form, eg in hydrogenated form. The modification, for example the hydrogenation, may be carried out before or after the incorporation of the fatty acid into the compound of formula (I).

In a preferred embodiment, the washing, cleaning or pretreatment agent comprises at least one fatty acid ester in which R is derived from a C ₈ -C ₂₀ fatty acid, ie in which R is a C ₇ -C ₁₉ hydrocarbon radical. In a preferred embodiment, the washing, cleaning or pretreatment agent comprises at least one fatty acid ester in which R is derived from a fatty acid selected from the group consisting of myristic, palmitic, stearic, oleic and linoleic acids or mixtures from that. Here, R can be present in hydrogenated or unhydrogenated form. The washing, cleaning or pretreatment agent preferably comprises at least one fatty acid ester of the formula (I) in which R derives from palmitic acid or oleic acid, ie R stands for an nC ₁₅ H ₃₁ or nC ₁₇ H ₃₃ radical. In one embodiment, the washing, cleaning or pretreatment agent comprises at least one fatty acid ester in which R is derived from the fatty acid mixture contained in coconut oil. More preferably, the washing, cleaning or pretreatment agent comprises at least one fatty acid ester in which R of Palmitic acid or oleic acid, and at least one fatty acid ester in which R is derived from the fatty acid mixture contained in coconut oil. More preferably, the washing, cleaning or pretreatment agent comprises at least one fatty acid ester in which R is derived from the hydrogenated or unhydrogenated form of the fatty acid mixture contained in palm oil or from the hydrogenated or unhydrogenated form of a fatty acid contained therein, and at least one fatty acid ester in which R is derived from the fatty acid mixture contained in coconut oil.

In a preferred embodiment, the washing, cleaning or pretreatment agent according to the invention comprises at least one fatty acid oligoester, where R is derived from a C ₁₆ -C ₁₈ fatty acid, ie has a C ₁₅ -C ₁₇ hydrocarbon radical. In a preferred embodiment, the washing, cleaning or pretreatment agent according to the invention comprises at least one fatty acid oligoester according to formula (I) wherein R is derived from palmitic, margarine, stearic, palmitoleic, petroselin, oil, elaidin, vaccinates -, or linoleic acid. The washing, cleaning or pretreatment agent preferably comprises at least one fatty acid oligoester of the general formula (I) wherein R is derived from the fatty acid mixture contained in palm oil or R is derived from the hydrogenated or unhydrogenated form of the fatty acid mixture contained in palm oil or from the hydrogenated or unhydrogenated one Derives form of a fatty acid contained therein.

The fatty acids contained in palm oil include palmitic acid (44.3%), stearic acid (4.1%), myristic acid (1.0%), oleic acid (38.7%) and linoleic acid (10.5%).

The fatty acids contained in coconut oil include caprylic acid (9%), decanoic acid (10%), lauric acid (52%), myristic acid (19%), palmitic acid (11%) and oleic acid (8%).

Preferably, R is derived from oleic acid, ie the fatty acid oligoester is a trioleate.
In a preferred embodiment, the fatty acid oligoester of general formula (I) is a glycerol, 2,2-bis (hydroxymethyl) -1,3-propanediol, preferably a trimethylolpropane triester, in which R is of palmitic, margarine, Stearic, palmitoleic, petroselin, oil, elaidin, vaccine, or linoleic acid or mixtures thereof. In another preferred embodiment, the fatty acid oligoester of general formula (I) is a trimethylolpropane triester in which R is derived from oleic acid, ie, a trimethylolpropane trioleate.

The washing, cleaning or pretreatment agent according to the invention may comprise more than one fatty acid oligoester according to 1). The washing, cleaning or pretreatment agent may comprise at least two fatty acid oligoesters as described in 1). Here, preferably at least one of the fatty acid oligoesters is a trimethylolpropane triester. Preferably, at least one of the esters is a trimethylolpropane triester in which R is derived from a C ₁₆ -C ₁₈ fatty acid. In a preferred embodiment, the washing, cleaning or Pretreatment agent only a fatty acid oligoester, preferably a C ₁₆ -C ₁₈ fatty acid oligoester of trimethylolpropane.

The fatty acid oligoesters of the washing, cleaning or pretreatment agent of the invention should preferably be water-soluble. Depending on the structure and properties of the HC scaffold and the fatty acid from which R is derived, it may be necessary to modify the water solubility of the fatty acid ester. In essence, any polyethylene glycol and / or polypropylene glycol structural fragment that provides the desired degree of water solubility can be used. Suitable polyethylene glycol and / or polypropylene glycol structural fragments are preferably structural fragments of ethylene oxide units and structural fragments of ethylene oxide and propylene oxide units, having a maximum proportion of 50% by weight of propylene oxide units, in particular a maximum proportion of 40% by weight of propylene oxide units. Units, more preferably a maximum proportion of 30 wt .-% of propylene oxide units, based on the weight of said structural fragment.

EO is an ethyleneoxy radical derived from ethylene oxide and PO is a propyleneoxy radical derived from propylene oxide.

For each residue independently, k and h represent the number of residues EO and PO contained in said residue, and independently represent a number from 1 to 500, especially from 1 to 250. For example, k and h can each independently be independently and independently are from 1 to 350, from 1 to 200, from 1 to 180, from 1 to 160, from 1 to 150, from 1 to 130, from 1 to 120, from 1 to 100.

For each residue independently, a and b denote the number of residues EO and PO contained in said residue, and independently represent 0 or a number from 1 to 500, especially from 1 to 250. For example, a and b can be independently and independently for each residue each represent a number from 1 to 400, from 1 to 300, from 1 to 200, from 1 to 150, from 1 to 125, from 1 to 115.

The total number of EO and PO units, i. (all a + all b + all k + all h), per fatty acid ester of the formula (I) is preferably from 50 to 2000, in particular from 50 to 1000, particularly preferably from 30 to 700, more preferably from 50 to 800 , most preferably from 100 to 750, more preferably from 120 to 700. Preferably, the total number of EO and PO units per fatty acid ester of formula (I) is from 50 to 350, for example 150.

The ratio of all EO units in compounds of the formula (I) to the number of all PO units is preferably in the range from 500: 1 to 2: 1, in particular in the range from 250: 1 to 2: 1, in particular Range from 180: 1 to 3: 1 or from 100: 1 to 3: 1, preferably in the range from 50: 1 to 5: 1, more preferably in the range from 20: 1 to 10: 1, for example 12: 1.

In a preferred embodiment, the number of all EO units in the triester according to the invention is greater than the number of all PO units. The total number of all EO units is preferably from 10 to 2000, in particular from 50 to 1000, preferably from 80 to 180, for example 120. The total number of all PO units is preferably 0 to 5000 or 0 to 2000, in particular 3 to 500 or to 100, preferably 6 to 60 or 6 to 30, in particular 8 to 15, for example 10.

worin

• R¹, R² und R³ jeweils unabhängig voneinander für einen Rest der Formel (IIa) stehen,
  
  worin
  • EO für einen Ethylenoxy-Rest abgeleitet von Ethylenoxid steht,
  • PO für einen Propylenoxy-Rest abgeleitet von Propylenoxid steht,
  • für jeden Rest unabhängig k und h die Anzahl der in besagtem Rest enthaltenen Reste EO und PO bedeuten und unabhängig voneinander für eine Zahl von 0 bis 500, insbesondere von 0 bis 250, stehen,
  • R für einen geradkettigen oder verzweigten, gesättigten oder ungesättigten C₄-C₄₉-Kohlenwasserstoffrest steht,
• R⁷ aus der Gruppe bestehend aus H, -OH, -O-R⁸, ein gegebenenfalls mit einer oder mehreren Gruppen -O-R⁸ substituiertes C₁- oder C₂-C₅ Alkyl, wobei jedes R⁸ unabhängig voneinander für Wasserstoff oder einen Rest der Formel (IIb) steht,
  
  • für jeden Rest unabhängig a und b die Anzahl der in besagtem Rest enthaltenen Reste EO und PO bedeuten und unabhängig voneinander für 0 oder eine Zahl von 20 bis 500, insbesondere von 50 bis 250, stehen,
• m, n, und p unabhängig voneinander für 0, 1, 2, oder 3 stehen,
• die Summe von m + n + p ≥ 2 ist,
• m, n, p und R⁷ so gewählt sind, dass das resultierende Kohlenwasserstoffgerüst 3 bis 8 Kohlenstoffatome besitzt,
• R⁴ für ein Wasserstoffatom oder falls m > 1 jedes R⁴ unabhängig voneinander für H oder -O-R⁹ steht, wobei jedes R⁹ unabhängig voneinander für Wasserstoff oder einen Rest der Formel (IIb) steht, und wobei die -OR¹-Gruppe und eine -OR⁹-Gruppe nicht an das gleiche Kohlenstoffatom des Kohlenwasserstoffgerüsts gebunden sind,
• R⁵ für ein Wasserstoffatom oder falls n > 1 jedes R⁵ unabhängig voneinander für H oder -O-R¹⁰ steht, wobei jedes R¹⁰ unabhängig voneinander für Wasserstoff oder einen Rest der Formel (IIb) steht, und wobei die -OR²-Gruppe und eine -OR¹⁰-Gruppe nicht an das gleiche Kohlenstoffatom des Kohlenwasserstoffgerüsts gebunden sind,
• R⁶ für ein Wasserstoffatom oder falls p > 1 jedes R⁶ unabhängig voneinander für H oder -O-R¹¹ steht, wobei jedes R¹¹ unabhängig voneinander für Wasserstoff oder einen Rest der Formel (IIb) steht, und wobei die -OR³-Gruppe und eine -OR¹¹-Gruppe nicht an das gleiche Kohlenstoffatom des Kohlenwasserstoffgerüsts gebunden sind,

mit der Maßgabe, dass nicht mehr als 4 Kohlenstoffatome zwischen zwei direkt an das Kohlenwasserstoffgerüst gebundenen Sauerstoffatomen vorliegen.In a preferred embodiment of the invention, the 1) at least one fatty acid oligoester has the formula (Ia)

wherein

• R ^1, R ² and R ³ are each independently a radical of the formula (IIa),
  
  wherein
  • EO is an ethyleneoxy radical derived from ethylene oxide,
  • PO is a propyleneoxy radical derived from propylene oxide,
  • independently of one another k and h denote the number of radicals EO and PO contained in said radical and independently of one another represent a number from 0 to 500, in particular from 0 to 250,
  • R is a straight-chain or branched, saturated or unsaturated C ₄ -C ₄₉ -hydrocarbon radical,
• R ^{7 is selected} from the group consisting of H, -OH, -OR ⁸ , a C ₁ - or C ₂ -C ₅ -alkyl optionally substituted by one or more -OR ⁸ groups, each R ⁸ independently of one another representing hydrogen or a radical of Formula (IIb) stands,
  
  • independently of one another, a and b denote the number of radicals EO and PO contained in said radical and represent, independently of one another, 0 or a number from 20 to 500, in particular from 50 to 250,
• m, n, and p are independently 0, 1, 2, or 3,
• the sum of m + n + p ≥ 2,
• m, n, p and R ⁷ are selected so that the resulting hydrocarbon skeleton has 3 to 8 carbon atoms,
• R ^{4 represents} a hydrogen atom or if m> 1, each R ^{4 is} independently H or -OR ⁹ , each R ^{9 being} independently hydrogen or a radical of formula (IIb), and wherein -OR ¹ and an -OR ⁹ group is not attached to the same carbon atom of the hydrocarbon skeleton,
• R ^{5 represents} a hydrogen atom or, if n> 1, each R ⁵ independently represents H or -OR ¹⁰ , wherein each R ^{10 is} independently hydrogen or a radical of formula (IIb), and wherein the -OR ² group and an -OR ¹⁰ group is not attached to the same carbon atom of the hydrocarbon skeleton,
• R ^{6 represents} a hydrogen atom or, when p> 1, each R ⁶ independently represents H or -OR ¹¹ , wherein each R ¹¹ independently represents hydrogen or a radical of formula (IIb), and wherein the -OR ³ group and an -OR ¹¹ group is not attached to the same carbon atom of the hydrocarbon skeleton,

with the proviso that not more than 4 carbon atoms are present between two oxygen atoms directly attached to the hydrocarbon backbone.

In the formulas (Ia), (IIa) and (IIb), EO and PO and R, a, b, k, and h are as defined above for formula (I).

In structure (Ia), R ^{7 is} a radical selected from the group consisting of H, -OH, -OR ⁸ , a C ₁ - or C ₂ -C ₅ optionally substituted with one or more groups -OR ⁸ Alkyl, wherein each R ^{8 is} independently hydrogen or a radical of formula (IIb). The term C ₁ - or C ₂ -C ₅ alkyl is to be understood as meaning a straight-chain or branched alkyl group. C ₁ - or C ₂ -C ₅ alkyl may be selected from the group consisting of a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl , n-pentyl, t-pentyl, neopentyl (2,2-dimethylpropyl), isopentyl (3-methylbutyl), s -pentyl (1-methylbutyl), and 3-pentyl (1 Ethylpropyl) radical. In a preferred embodiment, R ^{7 is} a radical selected from the group consisting of H, -OH, -OR ⁸ , a C ₁ - or C ₂ -C ₅ -alkyl. In a most preferred embodiment, R ^{7 is} a A radical selected from the group consisting of H, a C ₁ or C ₂ -C ₅ alkyl. In one embodiment, R ^{7 is} selected from the group consisting of H, a methyl radical, an ethyl radical, -OH, and -OR ⁸ . In one embodiment, R ^{7 is} H. In one embodiment, R ^{7 is} methyl. In one embodiment, R ^{7 is} an ethyl radical.

When R ^{7 is} a C ₁ or C ₂ -C ₅ alkyl radical, one or more oxygen atoms (each in the form of a -OH or -OR ⁸ group) may optionally be attached to R ⁷ . The oxygen atoms may be located at any possible position of the particular residue, with no more than 4 carbon atoms present between two oxygen atoms attached to the framework. The radical R ⁷ may be, for example, a C ₁ - or C ₂ -C ₅ alkyl group to which 0 to g oxygen atoms are substituted, g being the number of carbon atoms of the radical R ⁷ . In one embodiment, R ^{7 is} a C ₁ or C ₂ -C ₅ alkyl group to which an oxygen atom is attached. In one embodiment, R ^{7 is} a C ₂ -C ₅ alkyl group to which two oxygen atoms are attached. In one embodiment, R ^{7 is} a C ₂ -C ₅ alkyl group to which three oxygen atoms are attached. In a preferred embodiment, R ^{7 is} a C ₁ - or C ₂ -C ₅ alkyl group to which no oxygen atoms are bonded, in particular ethyl or methyl, most preferably ethyl.

In the chains denoted m, n, and p, m, n, and p are independently 0, 1, 2, or 3, the sum of m + n + p being ≥ 2 and not more than 4 carbon atoms between two may be present bound to the skeleton oxygen atoms.

R ⁴ represents a hydrogen atom or if m> 1, each R ⁴ independently represents H or -OR ⁹ , wherein each R ^{9 is} independently hydrogen or a radical of formula (IIb), and wherein the -OR ¹ group and an -OR ⁹ group are not attached to the same carbon atom of the hydrocarbon backbone. Preferably m is 0 or 1 and thus R ^{4 is} a hydrogen atom.

R ⁵ represents a hydrogen atom or, when n> 1, each R ⁵ independently represents H or - OR ¹⁰ , wherein each R ^{10 is} independently hydrogen or a radical of formula (IIb), and wherein the -OR ² group and an -OR ¹⁰ group are not attached to the same carbon atom of the hydrocarbon skeleton. Preferably, n is 0 or 1 and thus R ^{5 is} a hydrogen atom.

R ⁶ represents a hydrogen atom or, if p> 1 each R ⁶ is independently H or -OR ¹¹ wherein each R is independently hydrogen or a radical of formula (IIb) ^11, and wherein the -OR ³ group and an -OR ¹¹ group are not attached to the same carbon atom of the hydrocarbon skeleton. Preferably, p is 0 or 1 and thus R ^{6 is} a hydrogen atom.

Within the framework of the abovementioned restrictions, it is also possible independently of each of the methylene groups of the chains denoted by m, n or p to be bonded to an oxygen atom, ie within the above limits the radicals R ⁴ , R ⁵ , R ^{6 may} each represent -OR ⁹ , -OR ¹⁰ , -OR ¹¹ stand. Thus, no, one, two, or three of the chains can have more than one oxygen atom attached to them. In one embodiment, an oxygen atom is not bound to any of the chains denoted m, n, and p, ie, all of the chains designated m, n, and p have only the oxygen atoms shown in structure (la). In one embodiment, more than one oxygen atom is attached to one of the chains designated m, n, and p. In one embodiment, more than one oxygen atom is attached to two of the chains designated m, n, and p. In one embodiment, more than one oxygen atom is attached to all three of the chains designated m, n, and p.

In a preferred embodiment, in each of the radicals R ¹ , R ² and R ³ independently of one another k and h are at least 1 and in each of the radicals R ¹ , R ² and R ³ independently of one another k and h each have an average value of 1 to 500 , preferably from 1 to 200, especially from 1 to 120, or from 10 to 120. Preferably, the ratio between k and h is from 500: 1 to 1: 500, preferably from 200: 1 to 1: 200, especially from 120: 1 to 1: 120, or from 120: 10 to 10: 120.

Preferably suitable polyethylene glycol and / or polypropylene glycol structural fragments of the formulas (IIa) and (IIb) are preferably structural fragments of ethylene oxide units and structural fragments of ethylene oxide and propylene oxide units, with a maximum proportion of 50 wt .-% of propylene oxide units, in particular a maximum Proportion of 40 wt .-% of propylene oxide units, particularly preferably a maximum proportion of 30 wt .-% of propylene oxide units, based on the weight of said structural fragment.

For each residue independently, k and h represent the number of residues EO and PO contained in said residue, and independently represent a number from 1 to 500, especially from 1 to 250. For example, k and h can each independently be independently and independently are from 1 to 350, from 1 to 200, from 1 to 180, from 1 to 160, from 1 to 150, from 1 to 130, from 1 to 120, from 1 to 100.

For each residue independently, a and b denote the number of residues EO and PO contained in said residue, and independently represent 0 or a number from 1 to 500, especially from 1 to 250. For example, a and b can be independently and independently for each residue each represent a number from 1 to 400, from 1 to 300, from 1 to 200, from 1 to 150, from 1 to 125, from 1 to 115.

The total number of EO and PO units, i. (all a + all b + all k + all h) per fatty acid ester of the formula (Ia) is preferably from 50 to 2000, in particular from 50 to 1000, more preferably from 30 to 700, more preferably from 50 to 800 , most preferably from 100 to 750, more preferably from 120 to 700. Preferably, the total number of EO and PO units per fatty acid ester of the formula (Ia) is from 50 to 350, for example 150.

The ratio of all EO units in compounds of the formula (Ia) to the number of all PO units is preferably in the range from 500: 1 to 2: 1, in particular in the range from 250: 1 to 2: 1, in particular in the range from 180: 1 to 3: 1 or from 100: 1 to 3: 1, preferably in the range from 50: 1 to 5: 1, particularly preferably in the range from 20: 1 to 10: 1, for example 12: 1.

In a preferred embodiment, the number of all EO units in the triester according to the invention is greater than the number of all PO units. The total number of all EO units is preferably from 10 to 2000, in particular from 50 to 1000, preferably from 80 to 180, for example 120. The total number of all PO units is preferably 0 to 5000 or 0 to 2000, in particular 3 to 500 or to 100, preferably 6 to 60 or 6 to 30, in particular 8 to 15, for example 10.

In the formula (Ib), the C 'atom corresponds to the C atom of the formula (Ia) bound to R ⁷ . Together, all of the carbon atoms directly bonded to each other via the C 'atom and the hydrogen atoms of the formula (Ib) bonded directly to them correspond to the C ₃ -C ₈ hydrocarbon skeleton KW of the formula (I). This also represents the hydrocarbon skeleton (skeleton) of the formula (Ia).

In a preferred embodiment, 3 to 5, preferably 3, oxygen atoms are bonded directly to the entire C ₃ -C ₈ skeleton (formula (Ib) or CW in formula (I)). In one embodiment, at least one, preferably one of the designations m, n, and p is 0. Preferably, at least one, preferably two, more preferably three of the terms m, n, and p are 1. In a preferred embodiment, R ^{7 is} H or a methyl radical, preferably an ethyl radical.

In a preferred embodiment, 3 oxygen atoms are bonded directly to the entire C ₃ -C ₈ skeleton and one of the terms m, n, and p is 0.

In a preferred embodiment, 3 oxygen atoms are bonded directly to the entire C ₃ -C ₈ skeleton and at least one, preferably two of the designations m, n, and p stand for 1.

In a preferred embodiment, 3 oxygen atoms are bonded directly to the entire C ₃ -C ₈ skeleton and all of the designations m, n, and p stand for 1.

In a preferred embodiment, 3 oxygen atoms are bonded directly to the entire C ₃ -C ₈ skeleton and R ⁷ is a methyl or ethyl radical, preferably H.

In a preferred embodiment, 3 oxygen atoms are bonded directly to the entire C ₃ -C ₈ skeleton and R ⁷ is H or a methyl radical, preferably an ethyl radical.

In a preferred embodiment, all of the designations m, n, and p are 1 and R ^{7 is} a methyl or ethyl radical, preferably H.

In a preferred embodiment, all of the designations m, n, and p are 1 and R ⁷ is H or a methyl radical, preferably an ethyl radical.

In a preferred embodiment, 3 oxygen atoms are bonded directly to the entire C ₃ -C ₈ skeleton; all of the designations m, n, and p for 1 and R ⁷ is a methyl or ethyl radical, preferably H.

In a preferred embodiment, 3 oxygen atoms are bonded directly to the entire C ₃ -C ₈ skeleton; all of the designations m, n, and p for 1 and R ⁷ is H or a methyl radical, preferably an ethyl radical.

In the C ₃ -C ₈ skeleton according to the invention, not more than 4 carbon atoms are present between two oxygen atoms bonded directly to the skeleton. Preferably, no more than 3 carbon atoms are present between two oxygen atoms directly attached to the backbone.

In a particularly preferred embodiment, R ⁴ , R ⁵ , R ⁶ , and R ^{7 are} H and m, n, and p are each 1. More preferably R ⁴ , R ⁵ and R ^{6 are} H, R ^{7 is} C ₂ (Ethyl radical) and m, n and p are each for 1.

The following formulas (III), (IV) and (V) represent examples of possible constellations of fatty acid oligoesters of the present invention. By way of example, m = n = p = 1, R is an ethyl radical and the fatty acid oleic acid. According to the invention, each of the structures (III), (IV) and (V) shown and exemplified are to be understood as a trimethylolpropane trioleate. Shown are only EO radicals. However, according to the invention, those structures are also included in which the individual fatty acid chains are not bound by EO radicals alone but via PO radicals alone or preferably via a structural unit comprising EO radicals and PO radicals to the hydrocarbon skeleton (preferably trimethylpropane).

The quantities of the substances contained in the present application, unless otherwise defined in wt .-%, based on the total weight of the composition. If ranges are specified, then the values in between are to be regarded as disclosed.

The washing, cleaning or pretreatment agent of the present invention contains the 1) at least one fatty acid ester, for example in a proportion of 0.1% by weight to 30% by weight, preferably from 0.1% by weight to 10% by weight %, especially from 0.2% to 5%, or from 0.5% to 3% by weight based on the total weight of the composition.

Furthermore, the washing, cleaning or pretreatment agent of the present invention comprises 2) at least one surfactant which is not a fatty acid oligoester according to 1). This means that the agent according to the invention can comprise a surfactant or mixtures of different surfactants. The at least one surfactant which is not a fatty acid oligoester according to 1) may be an anionic, nonionic, cationic or zwitterionic surfactant. The composition of the invention may therefore contain mixtures of these different classes of surfactants. Soaps are not counted among the surfactants for the purposes of the present invention.

The anionic surfactant (anionic surfactant) used are preferably sulfonates, sulfates, alkyl phosphates, anionic silicone surfactants and mixtures thereof.

Preferred surfactants of the sulfonate type are C _9-13 -alkylbenzenesulfonates, olefin-sulfonates, ie mixtures of alkene- and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are C _12-18 alkanesulfonates and the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable.

Suitable soaps are fatty acid soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

The anionic surfactants and the soaps may be in the form of their sodium, potassium, magnesium or ammonium salts. Preferably, the anionic surfactants are in the form of their sodium salts. Further preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine, monoethanolamine or methylethylamine.

Nonionic surfactants in the context of the present application are, for example, fatty alcohol alkoxylates. These may have a linear or branched alkyl radical. The degree of alkoxylation is preferably 3 to 9 alkoxyl groups (AO) per mole of fatty alcohol. Further nonionic surfactants are, for example, fatty alcohols with more than 12 EO (ethoxy groups). Examples include tallow fatty alcohol with 14EO, 25 EO, 30 EO or 40EO. Other suitable nonionic surfactants include alkoxylated fatty acid alkyl esters, fatty acid amides, alkyl polyglycosides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, N-methylglucamides, alkylphenol polyglycol ethers, amine oxides, and mixtures thereof.

The washing, cleaning or pretreatment agent according to the invention preferably has a pH (at 20 ° C.) in the alkaline range. Preferably, it is in the range of 7.5 to 11.0, preferably 7.8 to 10.0, more preferably 8.0 to 9.0.

The at least one surfactant of the washing, cleaning or pretreatment agent of the present invention, which is not a fatty acid oligoester according to 1), may also comprise cationic and / or zwitterionic surfactants. From an application point of view, the washing, cleaning or pretreatment agent preferably contains exclusively nonionic and anionic surfactants. Optionally contained cationic and / or zwitterionic surfactants are described in detail in the literature and thus the skilled person well known.

The washing, cleaning or pretreatment agent according to the present invention comprises the at least one surfactant 2) in a proportion of, for example, from 1% by weight to 50% by weight, preferably from 2% by weight to 40% by weight, especially from 5 wt% to 30 wt%, or from 7 wt% to 25 wt% based on the total weight of the agent.

According to the invention, the washing, cleaning or pretreatment, in addition to the components 1) and 2) contain other ingredients that further the performance and / or aesthetic properties of the washing, cleaning or pretreatment improve. In the context of the present invention, the washing, cleaning or pretreatment agent preferably additionally contains one or more substances from the group of builders, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfume compositions, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils , Soil release polymers, grayness inhibitors, shrinkage inhibitors, wrinkle inhibitors, dye transfer inhibitors, other antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, softening components, skin care agents , Detergency-enhancing polymer ("booster polymers") and UV absorbers.

Particularly preferred additional ingredients are builders, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfume compositions, fluorescers, dyes, hydrotopes, foam inhibitors, soil release polymers, grayness inhibitors, dye transfer inhibiting agents, plasticizing components, UV absorbers and mixtures thereof.

As builders which may be present in the washing, cleaning or pretreatment agent, in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances may be mentioned.

Organic builders which may be present in the washing, cleaning or pretreatment agent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof, and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

However, preference is given to using soluble builders, for example acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol, in the liquid detergents or cleaners.

As an additive, the washing, cleaning or pretreatment agent of the invention may contain at least one enzyme. Cellulases are particularly suitable. For cellulases, synonymous terms may be used, especially endoglucanase, endo-1,4-beta-glucanase, carboxymethylcellulase, endo-1,4-beta-D-glucanase, beta-1,4-glucanase, beta-1,4-endoglucan hydrolase , Celludextrinase or Avicelase. Crucial for determining whether an enzyme is a cellulase according to the invention is its ability to hydrolyze 1,4-.beta.-D-glucosidic bonds in cellulose.

Cellulases (endoglucanases, EG) which can be synthesized according to the invention comprise, for example, the fungal cellulase preparation rich in endoglucanase (EG) or its further developments, which is offered by the company Novozymes under the trade name Celluzyme®. Endolase® and Carezyme®, also available from Novozymes, are based on the 50 kD EG or 43 kD EG from Humicola insolens DSM 1800. Further commercial products of this company are Cellusoft®, Renozyme® and Celluclean®. Further usable are, for example, cellulases available from the company AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®, which are based, at least in part, on the 20 kD-EG of melanocarpus. Other cellulases from AB Enzymes are Econase® and Ecopulp®. Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, those derived from Bacillus sp. CBS 670.93 is available from the company Danisco / Genencor under the trade name Puradax®. Other usable commercial products of the company Danisco / Genencor are "Genencor detergent cellulase L" and IndiAge®Neutra.

Also variants of these enzymes obtainable by point mutations can be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants described in International Publication WO 98/12307 Cellulases from Melanocarpus, in particular Melanocarpus albomyces, disclosed in the international publication WO 97/14804 Cellulases of the EGIII type from Trichoderma reesei disclosed in the European patent application EP 1 305 432 and variations obtainable therefrom, in particular those disclosed in the European patent applications EP 1240525 and EP 1305432 , as well as cellulases, which are disclosed in the international Offenlegungsschriften WO 1992006165 . WO 96/29397 and WO 02/099091 , The respective disclosure is therefore expressly referred to, or the disclosure content of which in this respect is therefore expressly included in the present patent application.

Washing, cleaning or pretreatment agents which are particularly preferred according to the invention are characterized in that at least one cellulase from Melanocarpus sp. or Myriococcum sp. 20K cellulase or those having homology in excess of 80% (more preferably greater than 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90%) , 5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5 %, 97%, 97.5%, 98%, 98.5%, 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99, 6%, 99.7%, 99.8%, 99.9%).

The from Melanocarpus sp. or Myriococcum sp. 20K cellulase available is from the international patent application WO 97/14804 known. It has as described there a molecular weight of about 20 kDa and has at 50 ° C in the pH range of 4 to 9 at least 80% of their maximum activity, while still maintaining almost 50% of the maximum activity at pH 10. It can, as also described there, be isolated from Melanocarpus albomyces and produced in genetically engineered Trichoderma reseei transformants. Also useful in the present invention are cellulases having a homology of greater than 80% (more preferably greater than 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%) %, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5% , 99.6%, 99.7%, 99.8%, 99.9%) to 20K cellulase.

K20 cellulase is preferably used in amounts such that a composition of the present invention has a cellulolytic activity of from 1 NCU / g to 500 NCU / g (determinable by the hydrolysis of 1 wt% carboxymethylcellulose at 50 ° C and neutral pH and determination of the reducing Sugar by dinitrosalicylic acid, as from MJ Bailey et al. in Enzyme Microb. Technol. 3: 153 (1981 ); 1 NCU defines the amount of enzyme which produces reducing sugars in an amount corresponding to 1 nmol of glucose per second), in particular from 2 NCU / g to 400 NCU / g and more preferably from 6 NCU / g to 200 NCU / g. In addition, the composition according to the invention may optionally contain further cellulases.

It is again particularly preferred according to the invention, in addition to at least one first cellulase from Melanocarpus sp. or Myriococcum sp. 20K cellulase or those having homology in excess of 80% (more preferably greater than 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90%) , 5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5 %, 97%, 97.5%, 98%, 98.5%, 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99, 6%, 99.7%, 99.8%, 99.9%) to employ at least one other second cellulase other than the first cellulase.

These second and any other cellulase other than the first can be cellulases described in the art. Preferably, it is a cellulase which is obtainable from Humicola insolens (Humicola grisea var. Thermoidea) and in particular from the strain Humicola DSM 1800. Furthermore, such cellulases can be part of the liquid composition according to the invention, which have a molecular weight of 50 kDa and an isoelectic point of 5.5 at a number of 415 amino acids and are obtained from Humicola insolens. Corresponding cellulases are, for example, in WO 96/27649 A1 described. The local disclosure on pages 4 and 5 under the heading "Cellulase enzymes" is expressly included in the present application.

In general, the enzymes contained in a composition of the invention may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation.

Compositions according to the invention may be added to the resulting enzymes in any form known in the art. These include in particular the solid preparations obtained by granulation, extrusion or lyophilization, advantageously as concentrated as possible, low in water and / or added with stabilizers. In an alternative dosage form, the enzymes may also 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 entrapped as in a solidified gel, or in such Core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

The proportion of cellulase in the liquid washing, cleaning or pretreatment agent according to the invention is preferably in the range from 0.1% by weight to 4% by weight, in particular from 0.1% by weight to 3% by weight, especially preferably from 0.1% to 2% by weight. The protein concentration can be determined by known methods, for example the bicinchonic acid method (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method ( Gornall AG, CS Bardawill and MM David, J. Biol. Chem. 177, 751-766, 1948 ).

The washing, cleaning or pretreatment agent according to the invention may contain, in addition to or instead of the cellulase, other enzymes known in the art or mixtures of enzymes.

Particularly suitable are those from the class of the hydrolases such as proteases, (poly) esterases, lipases, amylases, glycosyl hydrolases, hemicellulases, pectate lyase, xyloglucanase, cutinases, β-glucanases, oxidases, peroxidases, mannanases, perhydrolases, oxidoreductases and / or laccases.

The amount of enzyme or of the enzymes is preferably 0.01 to 10 wt .-%, preferably 0.12 to about 3 wt .-%, based on the total washing, cleaning or pretreatment agent. The enzymes are preferably used as enzyme liquid formulation (s).

If the washing, cleaning or pretreatment agent according to the invention is liquid, it preferably has a yield point. The yield stress refers to the smallest stress (force per area) above which a plastic substance behaves rheologically like a liquid. It is therefore given in Pascal (Pa). The yield strength of the composition according to the invention is in particular in the range from 0.1 to 1.0 Pa, preferably in the range from 0.2 to 0.9 Pa, in particular in the range from 0.3 to 0.8 Pa, at 25 ° C. The yield point is determined according to the invention by measurement with a rheometer, in particular with an AR 1000-N rheometer from Texas Instruments, at a temperature of 25 ° C. The rheometer AR 1000-N is an absolute measuring rheometer. In addition, the measured values output by the AR 1000-N rheometer are corrected with appropriate correction factors depending on the measuring geometries used, so that the AR 1000-N rheometer used determines reliable and reliable absolute measured values independent of the measuring geometry.

A liquid washing, cleaning or pretreatment agent according to the invention may contain, as an additional ingredient, in particular if it has a yield point, dispersed particles whose diameter along their greatest spatial extent is preferably 1 to 2000 μm. For the purposes of this invention, particles may be capsules, abrasives as well as powders, granules or compounds of compounds which are insoluble in the washing, cleaning or pretreatment agent, with capsules being preferred.

The term "capsule" on the one hand understood aggregates with a core-shell structure and on the other hand aggregates with a matrix. Core-shell capsules contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell of polymer (s).

Inside the capsules, sensitive, chemically or physically incompatible as well as volatile components (= active substances) of the liquid washing, cleaning or pretreatment agent can be enclosed stable in storage and transport. In the capsules, for example, optical brighteners, surfactants, complexing agents, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, Graying inhibitors, anti redeposition agents, pH adjusters, electrolytes, detergency boosters, vitamins, proteins, foam inhibitors, and UV absorbers. The fillings of the capsules may be solids or liquids in the form of solutions or emulsions or suspensions.

The capsules may have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their greatest spatial extent may be between 1 μm and 2000 μm, depending on the components contained within and their application.

Alternatively, it is also possible to use particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material. Such particles are also referred to as "matrix particles".

The matrix formation in these materials is, for example, via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the art as well as the production of particles with these matrix-forming materials. An exemplary matrix-forming material is alginate. For producing alginate-based particles is an aqueous alginate solution which also contains the active agent to be entrapped or the entrapped active ingredients, dripped and subsequently cured ³⁺ ions precipitation bath containing ions in a Ca ²⁺ or Al. Alternatively, other, matrix-forming materials can be used instead of alginate.

The capsules can be stably dispersed in the liquid washing, cleaning or pretreatment agents. Stable means that the detergents, cleaners or pretreatment agents are stable at room temperature for a period of at least 4 weeks, preferably at least 6 weeks, without the particles creaming or sedimenting in the composition.

The release of the active ingredients from the capsules is usually carried out by destruction of the shell or the matrix due to mechanical, thermal, chemical or enzymatic action.

When liquid, the washing, cleaning or pretreatment agents in a preferred embodiment contain capsules in which one or more fragrances are included.

When the washing, cleaning or pretreatment agents according to the invention are liquid, they preferably contain water as the main solvent. In addition, nonaqueous solvents can be added to the washing, cleaning or pretreatment agent. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or Glycol ethers, in such a concentration range in which they are miscible with water. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these solvents. However, it is preferred that the washing, cleaning or pretreatment agent contains an alcohol, in particular ethanol and / or glycerol, in amounts of between 0.5 and 5% by weight, based on the total washing, cleaning or pretreatment agent.

The washing, cleaning or pretreatment agent according to the invention is preferably provided in prefabricated containers (pouches). As a result, active ingredients can be packaged separately from each other. Furthermore, the dosage for a washing or cleaning or pretreatment course is optimal. In order that the detergents and / or cleaning agents and / or pretreatment agents then also come into effective contact with the objects to be cleaned, the respective containers must be water-soluble.

Preferably, the containers comprise at least one water-soluble material. Preferably, they consist of a water-soluble material. Water-soluble in the sense of the present invention means that the material dissolves in water or dispersed therein.
The water-soluble or water-dispersible material may comprise a polymer, a copolymer or mixtures thereof. Preferred water-soluble materials preferably comprise at least partially at least one of (acetalated) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, sulphate, carbonate and / or citrate substituted polyvinyl alcohols, polyalkylene oxides, acrylamides, cellulose esters, cellulose ethers, cellulose amides, cellulose, polyvinyl acetates , Polycarboxylic acids and their salts, polyamino acids or peptides, polyamides, polyacrylamides, copolymers of maleic acid and acrylic acid, copolymers of acrylamides and (meth) acrylic acid, polysaccharides, such as starch or guar derivatives, gelatin and under the INCI name Polyquaternium 2, Polyquaternium 17 , Polyquaternium 18 and Polyquaternium 27. Most preferably, the water-soluble material is a polyvinyl alcohol. Water-soluble polymers in the context of the invention are those polymers which are soluble in water at room temperature in excess of 2.5% by weight.

The fatty acid oligoesters of the present invention may be prepared by a variety of methods known to those skilled in the art. For example, the respective Fatty acids, the mono- or polyols contained in the hydrocarbon skeleton, as well as mono- or polyols containing the desired EO and / or PO structural fragment, are reacted with each other. Alternatively, the fatty acid oligoesters of the present invention may preferably be obtained by alkoxylating the fatty acid esters with mono- or polyols containing the desired EO and / or PO structural fragment.

The preparation of the washing, cleaning or pretreatment agent according to the invention is carried out by means of customary and known methods and processes. Thus, for example, the constituents of the washing, cleaning or pretreatment agent may be mixed in stirred kettles, water, nonaqueous solvent, acidic components and 1) at least one fatty acid oligoester and 2) at least one surfactant being initially charged. Subsequently, the other ingredients, preferably in portions added. Also possible is the production in a continuous process or in a combined batch-continuous process.

In a further embodiment, the present invention relates to a process for the preparation of the washing, cleaning or pretreatment composition comprising a process step in which the at least one fatty acid oligoester 1) and the at least one surfactant 2) are mixed.

Another aspect of the invention relates to a process for cleaning textiles or surfaces using a washing, cleaning or pretreatment agent according to the invention comprising a process step in which the washing, cleaning or pretreatment agent is brought into contact with a textile or a surface.

In a further embodiment, the present invention relates to the use of a fatty acid oligoester according to the invention as a whitening enhancer (lightness booster), in particular as a whiteness booster in a washing, cleaning or pretreatment agent.

For the purposes of the present invention, textiles are in particular textile fabrics, such as, for example, clothing, bath or laundry textiles. These may include natural and / or synthetic fibers such as silk, linen, cotton, polyester, polyamide or acetate fibers. The fibers can be treated or untreated. Furthermore, such textile fabrics are comprised, which consist of woven or non-woven materials such as felts or nonwovens.

Surprisingly, it has also been found that the use of the washing, cleaning or pretreatment agent of the present invention results in reduced wrinkling in the treated textiles as compared to the wrinkling of textiles treated with laundry, cleaning or cleaning compositions. or pretreatment agents which have no fatty acid oligoesters according to the invention.

In the context of the present invention, all of the abovementioned embodiments or preferred embodiments or the features described in each case can also be combined individually. Moreover, in the context of the present invention, the term "comprising" also covers the alternative in which the products / methods / uses, with respect to which the term "comprising" is used, consist exclusively of the subsequently described elements.

In the following exemplary embodiment, the washing, cleaning or pretreatment agent according to the invention is explained by way of example.

EXAMPLES

Unless otherwise specified, all processes and parameter measurements have been performed at room temperature (20 to 25 ° C).

The formulas below were prepared, in which the influence of fatty acid oligoesters was investigated as Weisskraftverstärker or graying inhibitor.

Example 1: Composition of the detergents

Example formulation 1 [% by weight] Example recipe 2 [% by weight] water ad 100 ad 100 boric acid 1.0 1.0 citric acid 3.2 3.2 Disodium 4,4'-bis (2-sulfostyryl) biphenyl 0.1 0.1 fatty acid oligoester - 2.0 ethanol - 2.0 1,2-propylene glycol 5.7 5.7 C _12-14 fatty alcohol ether sulfate with 2 units of ethylene oxide 9.0 9.0 C _10-13 -alkylbenzenesulfonic acid 7.0 7.0 C _12-18 fatty alcohol ether with 7 units of ethylene oxide 7.0 7.0 Polyesters of phthalic acid and ethylene oxide 1.3 1.3 coconut fatty acid 4.0 4.0 NaOH 2.95 2.95 Diethylenetriamine penta (methylene phosphonic acid), hepta sodium salt 0.7 0.7 foam breaker 0.04 0.04 Enzymes (amylase, protease, cellulase, mannanase, lipase) 1.7 1.7 Perfume 1.3 1.3 dye 0,002 0,002

The fatty acid oligoester used was Arlypon® TT from BASF. Arlypon® TT is known from the literature as a thickener in shampoos, shower gels and bath foams, which combines both associative and micellar thickening.

Example 2: Washing Tests and Whiteness Determination

Different white fabrics (WFK 10A, WFK 20A and WFK 30A) were washed for 60 minutes in addition to the commonly used soil monitors in a Miele washing machine type 318 at 16 ° d and 40 ° C in the main wash and their whiteness measured thereafter. The tissues are commercially available from "wfk Testgewebe GmbH". WFK 10 A fabric is made by "wfk Testgewebe GmbH" as "Standard Cotton" (standard cotton), WFK 20A as "Polyester / Cotton (65% / 35%)" (polyester / cotton 65% / 35%) and WFK 30A as "Polyester".

To measure the whiteness, a Datacolor DC600-2 meter was used and the whiteness was measured with a UV cut filter 2 (420 nm), a 30 mm aperture, without gloss and illuminant D65. The following results each represent an average of 6 measurements. recipes WFK 10A tissue WFK 20A fabric WFK 30A tissue Formulation 2 without fatty acid oligoester (comparative example) 81.2 77.8 81.6 Formulation 2 (according to the invention) 82.2 79.2 81.9

In all fabrics, an improvement in the whiteness can be seen when the detergent is used with the fatty acid oligoester according to the invention. This improvement is particularly outstanding on the WFK 20A fabric.

The pH of the compositions according to the invention (formulations 1 and 2) was 8.3.

The stains are liquid stains. These were each incorporated with a sponge in the textile surface fabric. At room temperature, the soils were dried and stored after drying the soiled textile fabric for a week. This storage was also carried out at room temperature.

Subsequently, the textile fabrics were cleaned in a standard washing machine in a standard program suitable for cooking and coloreds at a washing temperature of 40 ° C.

In each case, 6 textile fabrics were treated and cleaned with each of the mentioned soiling as described above. After cleaning, the textile fabrics were analyzed by photometric methods. The results obtained are the difference between the remission units obtained for the agent according to the invention and the remission units obtained for the reference (Δy = remission units EM 1 - remission units V 1). Positive values thus indicate a better cleaning performance of the agent according to the invention compared to the reference.

Claims (15)

Washing, cleaning or pretreatment comprising 1) at least one fatty acid oligoester of the formula (I)

wherein • KW is a linear or branched, saturated or unsaturated hydrocarbon skeleton having a number z of carbon atoms of 3, 4, 5, 6, 7 or 8, and wherein each carbon atom of the hydrocarbon skeleton is directly bonded to not more than one oxygen atom, EO is an ethyleneoxy radical derived from ethylene oxide, PO is a propyleneoxy radical derived from propylene oxide, For each residue, independently of one another, k and h denote the number of residues EO and PO contained in the said residue and independently of one another represent a number from 1 to 500, in particular from 1 to 250, For each residue independently a and b denote the number of residues EO and PO contained in said residue and independently represent 0 or a number from 1 to 500, in particular from 1 to 250, R is a straight-chain or branched, saturated or unsaturated C ₄ -C ₄₉ -hydrocarbon radical, • t is an integer from 3 to z, • s is an integer from 0 to (z-3), with the proviso that the sum of s + t stands for an integer from 3 to z, and
with the further proviso that there are not more than 4 carbon atoms between two oxygen atoms directly bonded with HC,
and 2) at least one surfactant which is not a fatty acid oligoester according to 1). A washing, cleaning or pretreatment composition according to claim 1, wherein the 1) at least one fatty acid oligoester has the formula (Ia)

wherein R ¹ , R ² and R ³ , independently of one another, are a radical of the formula (IIa)

wherein EO is an ethyleneoxy radical derived from ethylene oxide, PO is a propyleneoxy radical derived from propylene oxide, for each residue, independently of one another, k and h denote the number of radicals EO and PO contained in the said radical and independently of one another represent a number from 1 to 500, in particular from 1 to 250, R is a straight-chain or branched, saturated or unsaturated C ₄ -C ₄₉ hydrocarbon radical, R ^{7 is selected} from the group consisting of H, -OH, -OR ⁸ , a C ₁ - or C ₂ -C ₅ -alkyl optionally substituted by one or more -OR ⁸ groups, each R ^{8 being} independently hydrogen or a radical of the formula (IIb) stands,

for each residue, independently of one another, a and b are the number of residues EO and PO contained in the said residue and independently of one another are 0 or a number from 1 to 500, in particular from 1 to 250, • m, n, and p are independently 0, 1, 2, or 3, • the sum of m + n + p ≥ 2, M, n, p and R ⁷ are selected so that the resulting hydrocarbon skeleton has 3 to 8 carbon atoms, R ^{4 is} hydrogen or if m> 1, each R ^{4 is} independently H or -OR ⁹ , each R ^{9 being} independently hydrogen or a radical of formula (IIb), and wherein the -OR ¹ group and an -OR ⁹ group are not attached to the same carbon atom of the hydrocarbon skeleton, R ^{5 is} hydrogen or, when n> 1, each R ^{5 is} independently H or -OR ¹⁰ wherein each R ^{10 is} independently hydrogen or a radical of formula (IIb), and wherein the -OR ² group and an -OR ¹⁰ group are not attached to the same carbon atom of the hydrocarbon skeleton, R ^{6 represents} a hydrogen atom or, when p> 1, each R ⁶ independently represents H or -OR ¹¹ , wherein each R ^{11 is} independently hydrogen or a radical of formula (IIb), and wherein the -OR ³ group and an -OR ¹¹ group are not attached to the same carbon atom of the hydrocarbon backbone, with the proviso that not more than 4 carbon atoms are present between two oxygen atoms directly attached to the hydrocarbon backbone. Washing, cleaning or pretreatment agent according to one of the preceding claims, characterized in that the fatty acid oligoester in a proportion of 0.1% by weight to 30 wt .-%, preferably from 0.1 wt .-% to 10 wt .-%. based on the total weight of the agent. Washing, cleaning or pretreatment agent according to one of the preceding claims, wherein the at least one surfactant 2) in a proportion of 1 wt .-% to 50 wt .-%, preferably from 2 wt .-% to 40 wt .-%, especially from 5 wt% to 30 wt%, or from 7 wt% to 25 wt%, based on the total weight of the agent. Washing, cleaning or pretreatment agent according to one of the preceding claims, wherein 3 to 5, in particular 3 oxygen atoms are bonded directly to the C ₃ -C ₈ -hydrocarbon skeleton. Washing, cleaning or pretreatment agent according to one of the preceding claims, wherein the C ₃ -C ₈ skeleton contains 4 to 7, in particular 6 carbon atoms. Washing, cleaning or pretreatment agent according to one of claims 2 to 6, wherein R of the C ₃ -C ₈ skeleton is an unsubstituted C ₁ -C ₅ alkyl group, in particular an unsubstituted C ₂ alkyl group. A washing, cleaning or pretreatment composition according to any one of the preceding claims, wherein the fatty acid oligoester is a trioleate. A washing, cleaning or pretreatment agent according to any one of the preceding claims wherein in each of R ¹ , R ² and R ^3, independently of one another, k and h are at least 1 and wherein in each of R ¹ , R ² and R ³ independently k and h each have an average value of from 1 to 500, preferably from 1 to 200, especially from 1 to 120, or from 10 to 120. Washing, cleaning or pretreatment agent according to one of the preceding claims, wherein the ratio between k and h of 500: 1 to 1: 500, preferably from 200: 1 to 1: 200, especially from 120: 1 to 1: 120, or from 120: 10 to 10: 120. Washing, cleaning or pretreatment agent according to one of the preceding claims, wherein i) the total number of all EO units 10 to 2000, in particular 50 to 1000, preferably 80 to 180 and ii) the total number of all PO units is 0 to 5000 or 0 to 2000, in particular 3 to 500 or to 100, preferably 6 to 60 or 6 to 30, in particular 8 to 15. Washing, cleaning or pretreatment agent according to one of the preceding claims, wherein the agent is bleach-free. A washing, cleaning or pretreatment composition according to any one of the preceding claims, wherein the agent is liquid. A method for cleaning textiles or surfaces using a washing, cleaning or pretreatment agent according to any one of claims 1 to 12 comprising a process step in which the washing, cleaning or pretreatment agent is brought into contact with a textile or a surface. Use of a fatty acid oligoester of the formula (I)

wherein • KW is a linear or branched, saturated or unsaturated hydrocarbon skeleton having a number z of carbon atoms of 3, 4, 5, 6, 7 or 8, and wherein each carbon atom of the hydrocarbon skeleton is directly bonded to not more than one oxygen atom, EO is an ethyleneoxy radical derived from ethylene oxide, PO is a propyleneoxy radical derived from propylene oxide, For each residue, independently of one another, k and h denote the number of residues EO and PO contained in the said residue and independently of one another represent a number from 1 to 500, in particular from 1 to 250, For each residue independently a and b denote the number of residues EO and PO contained in said residue and independently represent 0 or a number from 1 to 500, in particular from 1 to 250, R is a straight-chain or branched, saturated or unsaturated C ₄ -C ₄₉ -hydrocarbon radical, • t is an integer from 3 to z, • s is an integer from 0 to (z-3), with the proviso that the sum of s + t stands for an integer from 3 to z, and
with the further proviso that there are not more than 4 carbon atoms between two oxygen atoms directly bonded with HC,
as a whitening enhancer, in particular as a whiteness enhancer in a washing, cleaning or pretreatment agent.