DD286181A5 - LIQUID, ENZYMETHIC DETERGENT - Google Patents

Abstract

The invention relates to a liquid, enzyme-containing detergent containing as a basic surfactant known nonionic surfactants, which are combined with commercially available anionic surfactants and a sulfobetaine / multifunctional sulfobetaine sulfone, a proteolytic or amylolytic enzyme, a hydrotrope, lower alcohols, polyhydric alcohols, ethylene glycols or diethylene glycol monobutyl ether , The liquid, enzyme-containing detergent has not only good washing action in the low temperature range fiber-restorative properties {detergent; liquid formulation, enzyme-containing; Laundry detergent; surfactant; Sulfobetainsulfon; sulfobetaine; Low temperature range}

Description

Field of application of the invention

The invention relates to a liquid enzyme-containing detergent formulation which has good low temperature detergency properties, fiber and fabric finish, and good color performance.

Characteristic of the known state of the art It is known that the incorporation of builders in liquid detergent formulations causes considerable difficulties. The sodium tripolyphosphate (NaTPP), which is most strongly represented in the powder products, has only been available in a few Exceptions are incorporated into liquid formulations. For example, ea is used in formulations of Procter & Gamble up to 46% by weight, based on the total formulation, of incorporated into aqueous liquid formulations

(DE-OS 26.46.127). In most known formulations, however, 20% by weight are not exceeded in analogous detergents. Mo och Domsjö AB succeeded in incorporating NaTPP and bleach in a liquid, essentially anhydrous formulation. These liquid dispersions correspond to the compositions of powdery heavy duty detergents.

A liquid, stable, concentrated, practically homogeneous full-washing and cleaning agent with a high level of viscosity

nonionic surfactants, one of which is an oxoethylate of a fatty alcohol having up to 15 carbon atoms and an EO content of 8 EO units, and the other is an oxoethylate of a fatty alcohol having at least 14 carbon atoms and containing up to 14 carbon atoms.

Is units, wherein the weight ratio of the nonionic surfactants to the anionic surfactant is in the range 1: 1 to 1: 1, (b)

a liquid organic carrier which may be an alcohol, and (c) water, as well as minor amounts of conventional ones

Detergent additives (foam control, optical brighteners, enzymes, ethanolamine) have been described in the patent DE- PS 26.58.073 presented. Due to the lack of builder this detergent is not to be regarded as a heavy duty detergent. With the improvement of mixing technology and sophisticated formulation work, it became possible to use liquid detergents

produce, which are equal to the powdered heavy duty detergents.

Thus, more recently (GB-PS 2,180,551.2.178.753,2.169.63,2.177.716 and 2,195,123, DE-OS 36.26.572 and 36.09.345)

liquid nonaqueous detergent formulations disclosed from balanced surfactant combinations i'z. B. ethoxylates with different EO chain length), builder salts, such as contained in powdered detergents, enzymes and with

Oxidation bleaches or reduction bleaches and bleach activators, if necessary. By addition

a so-called organic solubilizer (eg, diethylene glycol monobutyl ether), the viscosity is lowered to improve the handling of these products. The so formulated liquid non-aqueous detergent show the same performance as powdered products (heavy duty detergent). Due to its complicated formulation, a high level of mixing technology is required and, secondly, high quality requirements are to be met

Substances, which requires an excellent manufacturing process for the surfactants and additives. On water was added

Therefore, these formulations omitted, since only then the developed formulations are stable, if there is no

Zorsetzungserscheinungen comes. In the composition surfactant combination, builder, bleach, activator and enzyme

However, the stability can only be achieved if the work is largely anhydrous.

The use of enzymes in detergents is not a novelty of the last 10 years dar. After already in the 40s over

Their use in corresponding detergent formulations was researched, the enzyme used in 1969/70 reached a

Highlight (Soap, Cosmet., Former Specialties, New York 59 (1983) 5, pp. 48 to 50F). Investigations into the use of enzymes in detergents made in recent years are clear

show that the effect of the enzymes can compensate for the lack of detergent phosphates to a certain extent, and that, on the other hand, with enzyme use, better washing results can be achieved in the low-temperature range (A. A. Starace, J. Arner, Oil Chemists, Soc., Champaign 60 [1983] 9, pp. 1672-1675; Ch. A. Starace; HAPPI,

Household Pers. Prod. Ind. 20 [1983] 3, pp. 49 to 51; S. Tayota; Funtai to Kogyo 14 (1983) 7, pp. 45 to 52). Bacterial proteases (alcalases) purchased from Novo, Denmark, for use at pHs up to 12

marketed under the name Esperase, can be stably used in liquid detergent formulations when the water content is below 60% by weight of the liquid products. A rapid loss of enzyme activity occurs in the

Contact with complexing agents such as NaTPP and Nitrilotnacetat as well as in the presence of substances with active Ch'or or Oxygen. Furthermore, it could be found in studies on the effect of detergent enzymes that in

38'C b'ie double enzyme concentration required for the same effect as in 5O ⁰ C (Ch A. Starace;. J. Amer Oil Chemists'.

Soc Champaign 60 [1983] 5, pp. 1025-1027). Furthermore, in a wealth of publications, the most diverse enzymes for use in liquid Detergent formulations presented. The result of these investigations is: replace the enzymes in liquid systems

partly the missing builders; their effect in the low-temperature range is particularly emphasized (G. Jensen;

Comun. Jörn. Com. Deterg. 15 (1984), p.571 to 596; P. Nedkov, D. Toushek and Sh. Takov; Chim. Ind., Sofia [1983] 3,120 to 122; J.Novak; Prum. Potravin 35 H 984] 2, pp. 104 to 106; T. Hashimoto, T. Fujii u. M. Minagawa; Yukagaku, Tokyo 35 [1986] 4, p. 293 Emerging problems, such as the maintenance of activity and storage stability, depend on the used Wsschmittelformiilierungen and the respective enzymes from. Object of the invention

The object of the invention is to develop a liquid, storage-stable, enzyme-containing detergent formulation which has good utility in terms of low temperature detergency, fiber and fabric finishing and good color fastness.

Explanation of the essence of the invention

The invention has for its object to find a surfactant combination that ensures a liquid, storage-stable, enzyme-containing detergent formulation. The object is achieved according to the invention by combining known nonionic surfactants as the basic surfactant with a sulfobetain mixture without customary builders with further additives, the newly developed detergent formulation having the following composition:

25 to 45% by weight of nonionic surfactants selected from the group of polyoxyethylene adducts or polyoxypropylene-polyoxyethylene adducts or mixtures thereof,

From 0.1 to 6% by weight of an anionic surfactant selected from the group of sulfonates,

From 2 to 6% by weight of N-C'i6H33 / C18H37-alkyl-N, N-bis (oxyethylene) -amine having from 5 to 15 EO units,

From 2 to 6% by weight of N-C16H33 / C18H37-alkyl N, N-bis (oxyethylene) -ammonio-propane sulphonate having from 2.5 to 15 EO units,

From 2% to 8% by weight of a multifunctional sulfobetainsulfone mixture,

2 to 10% by weight of hydrotrope or mixture of different hydrotropes,

From 10 to 20% by weight of an organic solvent or mixtures thereof,

0.01 to 2% by weight of enzyme preparation,

0.01 to 0.2% by weight of optical brightener,

0.01 to 0.1% by weight of dye,

- 0.01 to 0.3 Gev / .-% perfume,

- 0 to 56Gew .-% of an additive or additive mixture, pH adjustment with technical sodium hydroxide solution, ethanolamine or triethanolamine and compensation to 100 wt .-% with water.

As additives for the enzyme-containing liquid detergent can be used:

- Obls4Gew .-% Horn », toff,

From 0 to 0.5% by weight of a silicone oil from the group of the dimethylpolysiloxanes and

0 to 3% by weight of grayness inhibitor (phosphorylated starch product).

As a nonionic surfactant, oxyethylated fatty alcohol plate of chain length C-9 to C-18 having an average content of 8 to 16 EO units, a C-8 to C-13 alkylphonylpolyoxyethyleri of 8 to 15 EO units or of technical-ethoxylated. Fatty alcohol mixtures prepared by selective reduction of high acid unsaturated fatty acid mixtures to give the double bond, having an average of 16 to 18 carbon atoms and an average content of 5 to 15 EO units, and C-12 / C-14 Alcohol mixtures having an average PO content of 3 to 5 PO units and EO content of 2 to β EO units, can be used. C-9 to C-15 alkanesulfonates or C-12 to C-16 olefin sulfonates may be used as the anionic surfactant. Suitable hydrotropes for the liquid enzyme-containing detergent formulation are, according to the invention, low molecular weight organic compounds with an accumulation of polar groups. Especially the following compounds can be used:

Dimethylaminomethane bisphosphonic acid,

- citric acid,

- propane trisulfonic acid,

Propane-1,3-disulfone-2-sulfinic acid,

I.I.S-trimethyl-sulfomethyl-pyrrolidinium-betaine,

i.i-dimethyl-S-sulfonic acid methyl-sulfomethyl-pyrrolidinium-betaine,

1,1-dimethyl-3,4-disulfomethylpyrrolidinium betaine,

- Glucosf /,

- Glucic acid. Their mixtures can also be used.

The multifunctional Sulfobetainsulfongemisch 'inn in a .Eintopfverfahren * through the common and simultaneous reaction of maleic acid mono-N-alkylamides and time "uremonoalkylestern be manufactured with a Sulfobetainsulfinsäure. Thus, for example, a multifunctional Sulfobetainsulfongemisch by reaction of maleic anhydride with Fettelkoholon or fatty alcohol mixtures, ethoxylated fatty alcohols, oxyethylated Fettarr.inen and polyethylene glycols having molecular weights of 300C to 5000 and subsequent addition of 1,1-dimethyl-3-sulfinsäuremethyM-sulfomethyl-pyrrolidinium betains en this mixture are prepared.

Particularly suitable graying inhibitor in these formulations is phosphorylated starch, a reaction product Potato starch and sodium cyclotriphosphate. The use of organic solvents once has the task to obtain homogeneous Waschmittelformulierungon and

on the other hand, these influence the washing action as additives. Furthermore, it can be used to some extent

Foam to be regulated. For the Einsau in these formulations according to the invention are lower alcohols, such as Ethanol, isopropanol, n-propanol, polyhydric alcohols, such as glycerol, propanediol, or ethylene glycols, for example Triethylene glycol, or ethylene glycol monoether, such as diethylene glycol monobutyl ether, or mixtures thereof in question. In the established liquid detergent formulations can be without difficulty liquid proteolytic and

Install amylolytic enzyme preparations. Surprisingly, it was found that in these formulations after prolonged storage (8 months) the enzyme activity hardly changed. Were the formulations used from these formulations

Sulfobetaines (N-C16H33 / C18H37-alkyl-N, N-bis (oxyethylene) -ammonio-propanesulfonate, multifunctional Sulfobetainsulfongemisch) removed, then the enzyme activity decreased significantly after 4 months. The formulated, liquid detergents need no builders due to their composition; they are essentially

Water hardness independent and show a good cleaning effect in the low temperature range.

In addition to the good cleaning action in the low temperature range (40 to 60 ⁰ C), these developed Detergent formulations improved secondary wash properties. A fiber softening effect was observed

and there was a color refresh in dyed fibers. Surprising was that even already washed out

Colors again a fresh impression. Strong stains could be eliminated even at low temperatures

become.

The pH adjustment of 8.5 to 10 may be advantageous with technical sodium hydroxide solution, ethanolamine or triethanolamine

respectively.

Advantages of these enzyme-containing, liquid detergent formulations are:

- In these formulations, the proteolytic and amylolytic enzymes are long-term stabilized.

- The built-up liquid formulations are largely water hardness independent; they do not need builders in the usual sense.

- The nonionic used as a base surfactant is a product of commercial nature.

- Better color refreshment of dyed fibers is given; there are no faded colors when using optical brighteners.

- A fiber softening effect is achieved.

- Heavy soiling can be easily removed.

- With these formulations, the washing temperature can be reduced.

Atisfuhrungsbelspiele

BeUpIe11

26% by weight of ethoxylated fatty alcohol mixture of chain length C-1Ö having an unsaturated content in the chain and an average EO content of 16 EO units,

O.BGew .- '& AlkansulfonaMC g to C-IS-alkyl chain length),

3Gew% N.C16H33 / Ci8H37-alkyl-N, N-bis (axyethylene) -amine with 7 EO units, 2% by weight of N-C16H33 / C18H37-alkyl-N, N-bis (oxyethylene) -ammonio propanesulfonate with 3EO units, 6 wt% multifunctional sulfobetaine sulfone mixture (50% active solids content), 8 wt% dimethylaminomethane bisphosphonic acid,

10% by weight of triethylene glycol,

4% by weight of 1,2-propanediol,

0.05gow% optical brightener,

0.03% by weight of perfume oil,

0.02% by weight of dye,

1 Gow .-% phosphorylated starch product,

2% by weight of urea,

0.1% by weight of dimethylpolysiloxane, 0.4% by weight of amylolytic enzyme

(Maxamyl WL)

Adjustment to 100% by weight: The composition is adjusted to a pH of 9 with ethanolamine and diluted with water.

Example 2

26% by weight C-12 / C-14 alcohol mixture with an average content of 5 FO and 3 EO units, 2% by weight oxo alcohol mixture of 8 EO units per hydroxyl group,

0.5% by weight of alphaolefin sulfonate mixture of chain length C-12 to (M 8,

4% by weight of N-C16H33 / C18H37-alkyl-N, N-bis (oxyethylene) -amine having 15 EO units, 2% by weight of N-CieH33 / C18H37-alkyl-N, N-bis (oxyethylene) -ammonio propanesulfonate with 7 EO units, 3Gew .-% multifunctional sulfobetaine sulfone mixture,

4% by weight of dimethylaminomethane bisphosphonic acid,

2 wt .-% 1,1,3-trimethyl-4-sulfomethyl-pyrrolidinium betüin,

^ Wt. ^ Glycerol / diethylene-GemischimGew.-Verha'ltni? = 1: 1.2 wt.% Urea,

0.4% by weight of uimethylpolysiloxane,

0.4% by weight of proteolytic enzyme preparation (Maxatase LS),

0.6% by weight of phosphorylated starch product, 0.02% by weight of optical brightener, 0.15% by weight of perfume oil, 0.03% by weight of acid blue dye, compensation to 100% by weight: It is mixed with 33% strength technical sodium hydroxide solution adjusted to a pH of 10 and then diluted with water.

Belsple! 3

26% by weight oxyethylated fatty alcohol mixture of chain length C-18 having an unsaturated content in the chain and an average EO content of 15 EO units, 3% by weight alkanesulionate (C 9- to C-15 alkyl chain mixture), 5% by weight % N-C16H33 / C18H37-alkyl-N, N-bis (oxyethylene) -amine having 7 EO units, 2% by weight of N-CieH33 / C18H37-alkyl-N, N-bis (oxyethylene) -ammonio-propanesulfonate with 2 , 5 EO units, 8% by weight of multifunctional sulfobetainsulfone mixture (50% aqueous mixture), 5% by weight of dimethylaminomethane bisphosphonic acid,

5% by weight of 1,1-dimethyl-S-sulfinic methyl-sulfomethylpyrribdinium-betaine, 15% by weight of propanediol / n-propanol / glycerol mixture in a weight ratio = 1: 1: 1,

2% by weight urea, 0.5% by weight dimethyiphenylsiloxane, 0.6% by weight phosphorylated starch product,

1% by weight of protolytic enzyme preparation

(Maxatase LS),

0.03% by weight of optical brightener, 0.05% by weight of perfume oil, 0.02% by weight of acid-blueing agent, compensation to 100% by weight: triethanolamine is used to prepare a pH. 3, then the pH is increased to 9.5 with 33% technical sodium hydroxide solution and then diluted with water.

BelspleM

The composition and formulation instructions correspond to Example 1. Instead of the 26 wt .-% of ethoxylated fatty alcohol mixture of the chain length C-18 with an unsaturated portion In the chain and an average EO content of 15 EO units 26Gew .-% Nonylphenylpolyoxyethylen with 10 EO units used.

example

23% by weight oxyethylated furfural mixture of kevel length C-18 having an unsaturated content in the chain and an average EO content of 15 EO units, 4% by weight CH / CM alcohol mixture with an average content of 3 PO and 5 EO units , 0.6 wt% alpha olefin sulfonate of chain length C-12 to C-1 beta, 3Gew% N-CieH33 / C18H37 alkyl N, N-bis (oxyethylene) amine with 15 EO units, 2 wt. % N-CieH33 / C18H37-alkyl-N, N-bis (oxytriylene) -ammonio-propanesulfonate with 7 EO units,

6% by weight of multifunctional sulfobetaine sulfone mixture (50% aqueous mixture),

3% by weight of oimethylaminomethane bisphosphonic acid,

2 wt .-% 1,1-dimethyl-S-sulfinsfiuremethyM-sulfomethyl-pyrrolidinium-betaine, 3Gew .-% gluconic acid, 10Gow .-% triethylene glycol / 1,2-propanediol In the weight ratio ·> 2: 1 , 2% by weight of urea, 0.5% by weight of dimethylpolysiloxane, 1.6% by weight of phosphorylated starch product, 0.6% by weight of proteolytic enzyme preparation (Maxatase LS),

0.08% by weight of optical brightener, 0.1% by weight of perfume oil, 0.05% by weight of acid blue dye, compensation to 100% by weight: It is adjusted to a pH of 9 with ethanolamine and diluted with water.

Examples

The detergent formulation is constructed as Example 5; instead of the 23 wt .-% oxeihyliurten fatty alcohol mixtures of chain length C-18 with an unsaturated portion in the chain and an average EO content of 15 EO units 23 wt .-% tallow alcohol ethoxylate with 14 EO units are used.

Claims (9)

1. Liquid, enzyme-containing detergent, characterized in that it is made From 25 to 45% by weight of a nonionic surfactant selected from the group of polyoxyethylene adducts or polyoxypropylene-polyoxyethylene adducts or mixtures thereof, 0.1 to 5% by weight of an anionic surfactant selected from the group of sulfonates, 2. Liquid, enzyme-containing detergent according to claim 1, characterized in that as nonionic surfactant an ethoxylated fatty alcohol mixture of chain length C-9 to C-18 with an average EO content of 8 to 15 EO units, a C-8 · to C 13-Alkylphenylpolyoxyethylen having 8 to 15 EO units or technical ethoxylated fatty alcohol mixtures prepared by selective reduction of fatty acid mixtures with a high unsaturated acid content to obtain the double bonds and have an average of 16 to 18 carbon atoms and an average EO content of Have 5 to 15 EO units, as well as C-12 / C-14-alcohol mixtures having an average PO content of 3 to 5 units and an EO content of an average of 2 to 6 EO units is used. 2 to 10% by weight of hydrotrope or mixture of different hydrotropes, From 10 to 20% by weight of an organic solvent or mixtures thereof, 0.01 to 2% by weight of enzyme preparation, 0.01 to 0.2% by weight of optical brightener, 0.01 to 0.1% by weight of dye, 0.01 to 0.3% by weight of perfume, - 0 to 56Gew .-% of an additive or additive mixture, pH adjustment with technical sodium hydroxide solution, ethanolamine or triethanolamine and compensation to 100Gew .-% with water consists. From 2% to 8% by weight of a multifunctional sulfobetaine sulfone mixture, From 2 to 6% by weight of N-C16H33 / C18H37-alkyl N, N-bis (oxyethylene) -ammonio-propane sulphonate having from 2.5 to 15 EO units, From 2 to 6% by weight of N-C16H33 / C18H37-alkyl-N, N-bis (oxyethylene) -amine with 5 to 15 EO units, 3. Liquid, enzyme-containing detergent according to claim 1 and 2, characterized in that the anionic surfactant is a C-9 to C-15 alkanesulfonate or C-12 to C-16-olefinsulfonate is used. 4. Liquid, enzyme-containing detergent according to claim 1 to 3, characterized in that dafi as a multifunctional Sulfobetainsulfongemisch reaction products of maleic anhydride with fatty alcohols or fatty alcohol mixtures, ethoxylated fatty alcohols, oxyethylated fatty amines, fatty amines and polyethylene glycols with Molekularon from 3000 to 5000 and subsequent addition of the 1,1- Dimethyl-3-sulfinic acid-methyl-4-sulfomethyl-pyrrolidiniumbetains to this mixture, preferably the reaction product of maleic anhydride and technical Oxoalkohol the average composition of C13H 27 OH, ethoxylated animal body fat the average composition of C17 H 35 N (EOn) 2 with 3 EO units in the molecule, polyethylene glycol having a molecular weight of 4000 and distilled technical animal body fat amine of the average composition of C17 H 35 NH 2 and subsequent addition of the ii-dimethyl-S-sulfinic acid methylsulfomethyl-pyrro lidinium betains to this mixture. 5. Liquid, enzyme-containing detergent according to claim 1 to 4, characterized in that as hydrotrope organic short-chain molecules with an accumulation of polar groups, such as Dimethylaminomethanbisphosphonsäure, glucose, IIS-trimethyl ^ -sulfomethyl-pyrrolidiniumbetain, 1,1-dimethyl-3 sulfinic acid-methyl-4-sulfomethyl-pyrrolidinin-betaine, 1,1-dimethyl-3,4-disulfomethyl-pyrrolidinium-betaine, citric acid. Propanetrisulfonic acid, gluconic acid or mixtures thereof, preferably the Dimethylaminomethanbisphosphonsäure be used. 6. Liquid.enzymhaltiges detergent according to claim 1 to 5, characterized in that as organic solvent lower alcohols, such as ethanol, isopropanol, n-propanol, polyhydric alcohols, such as glycerol, propanediol, or ethylene glycols, for example triethylene glycol, or ethylene glycol, such as Diethylenglykolmonobutylether, or mixtures thereof are used. 7. Liquid, enzyme-containing detergent according to claim 1 to 6, characterized in that as additive 0 to 4% by weight of urea, 0 to 0.5% by weight of silicone oil from the group of the dimethylpolysiloxanes, 0 to 3% by weight of grayness inhibitor (phosphorylated starch product) or mixtures of these additives, is used. 8. Liquid, enzyme-containing detergent according to claim 1 to 7, characterized in that are used as the enzyme component proteolytic or amylolytic enzymes. 9. Liquid, enzyme-containing detergent according to claim 1 to 8, characterized in that the pH adjustment with technical sodium hydroxide, ethanolamine or triethanolamine revalued between 8 and 10 and compensation with Wisser to 100Gew .-%.