DE3344097C2 - Enzymes containing liquid detergent and cleaning agent - Google Patents

Description

The invention relates to an enzyme-containing liquid detergent composition, which is both for soaking and pre-washing as well as detergent for the main wash, and concerns a such agent, the mixtures of the enzymes protease and Amylase in certain ratios thus set contains that during the washing process a especially effective removal of dirt and stains is achieved.

There have hitherto been enzyme-containing liquid detergent Compositions have been known and noted. enzymes are mainly used in detergent compositions incorporated, because you look at the ability of proteolytic and amylolytic enzymes for dislocation of protein and starch substances that are in and on soiled fabrics, effectively take advantage wants to make stains such as sauce stains, Blood stains, chocolate stains and the like be removed more easily during the washing process. However, the use of enzymatic substances, especially proteolytic enzymes suitable for detergent use are, relatively expensive. Even if she only are present in relatively small quantities, it is generally the most expensive components in a typical commercial liquid wash and detergents. In addition, one usually has one Excess of enzymes for a particular detergent Provide composition, because as a result of the known Instability of enzymes in aqueous compositions you need such an excess of enzyme in the recipe usually to the expected loss of enzyme activity  during longer storage times. This with the Use of enzymes in liquid detergents and cleaners associated disadvantages have so far a general widespread commercial use of such compositions hindering and deterrent stood in the way.

Mixtures of enzymes, e.g. B. proteases and amylases containing Detergent compositions are already several times been described. For example, in the US PS 36 30 930 describes a granulated detergent which contains about 0.5 to 20% of enzyme carrier granules, and the enzyme granulate consists of about 0.001 to 10% of the mixture of protease and amylase enzymes in one Weight ratio of protease to amylase from 50: 1 to 1: 5. In GB-PS 12 40 058 is a granulated detergent described that a mixture of protease and amylase Enzymes in a weight ratio of 30: 1 to 3: 1 protease to amylase, wherein the amylase in an amount from 0.0003 to 3% by weight, based on the detergent composition, is present in it. The US-PS 39 31 034 relates to a washing and cleaning agent granules, the alkaline protease and α-amylase enzymes in one Activity ratio of 100,000 to 400,000 novo-amylase Units of amylase per Anson units resulting in protease Contains mixture.

Accordingly, while the use of enzyme Mixtures in granulated detergents and cleaners in the patent literature in general, however The enzyme mixtures are as such in most Cases described so broad that they z. B. such Include mixtures in which the percentage to protease over 5 orders of magnitude may vary (GB-PS 12 40 058), or in which the percentage of  Amylase varies over 5 orders of magnitude can (US-PS 36 30 930). This reinforces the expert in the assumption that the stain removing effect is so works better, the bigger, within such broader Ranges, the amount of enzyme used. About that In addition, the aforementioned patents relate in the same way as the US-PS 39 31 034 specifically on such detergents and cleaners in granulated form and give the expert thus no reference to the Use of enzyme mixtures in liquid compositions.

The subject of the present invention is an enzyme containing liquid detergent and cleaner composition. This consists according to the invention of:

• (a) about 5 to 75% by weight of one or more surfactants, anionic, nonionic, cationic, ampholytic or zwitterionic surfactant or Detergent substances;
• (b) about 25 to 85% water; and
• (c) one consisting essentially of an alkaline protease Enzyme and an α-amylase enzyme existing enzyme Mixture containing these two enzymes in a ratio in enzyme activities of about 4,000 to 80,000 Novo Amylase units attached to α-amylase per Anson unit Protease containing relative amounts, wherein the protease is present in such an amount that per 100 g of total composition about 0.25 to 2.5 Anson units are located therein.

The invention further relates to a washing process for cleaning stained and / or soiled Materials characterized in that one these materials with an aqueous solution of the invention liquid detergent and cleaning agent in contact brings.  

It has surprisingly been found that the amount of alkaline Protease enzyme, usually for removal required by protein stains, quite considerably can be reduced when using this enzyme in combination with a specified for the agent according to the invention Amylase enzyme used.

This gives the invention a detergent and cleaner composition, the one equivalent to the previously known means or improved soil removal ability has, but compared to this a much less has elaborate recipe. Different from those in the existing detergent compositions present Enzyme mixtures in which proteases and amylases in quantity combined in very wide areas, was found that for washing and cleaning agents according to the invention envisaged enzyme mixtures a characteristic synergistic effect between protease and Have amylase and only these mixtures, the have the specified, closely defined activity ratio, include.

The activities of alkaline protease enzymes and α-Amylase enzymes are indicated in Anson units for protease or novo-amylase units for amylase. These units are commonly used by those skilled in the art Description of the activity under common conditions for enzyme formulations in which protease or amylase Enzymes are included.

In a preferred embodiment of the invention Detergents and cleaning agents are enzyme mixtures therein present, the alkaline protease and α-amylase in such Amounts containing 10 000 to 50 000 novo-amylase units to α-amylase per Anson unit of protease present are, even better, the activity ratio between  about 15,000 and 40,000 and is particularly desirable such a ratio of about 30,000 to 40,000 exists is.

The amount of liquid washing in a liquid according to the invention and detergent composition of existing enzyme Mixture depends to some extent on the amount of compositions added to the wash liquor is intended for detergents and cleaners are for use in automatic household washing machines in concentrations of about 0.15% in the wash solution is such an amount of mixture appropriate, by which contains about 0.25 to 2.5 Anson units of protease each 100 g detergent and cleaner composition, especially advantageously in 0.5 to 2.0 and especially desirable about 1.5 Anson units per 100 grams of composition is introduced.

As stated before, the activity of the alkaline Protease enzyme measured in Anson units. The Hemoglobin method for measuring Anson unit activity is a known procedure for determining the activity of proteolytic enzymes and is described in "Journal of General Physiology", Volume 22, pages 79 to 89 (1939). It is possible to measure the proteolytic Activity also the modified Anson-Hemoglobin method serve. The modified method is in the article "Alkali Resistant Enzymes for Detergents", S.R. Green, Soap and Chemical Specialties, pages 86, 88, 90, 94 and 133, May 1968. Used in this method in principle, the alkaline protease enzyme in the way in a buffered aqueous medium. At a selected pH under standard conditions denatured Hemaglobin substrate is consumed and one determines the amount of used material by one Color test with phenol reagent.  

The activity of the α-amylase enzyme is, as previously stated, measured in novo-amylase units. The standard procedure for measuring such novo units is a modification the SKB method (Sandstedt, Kneen & Blish, Cereal Chemistry 16, 712, (1939)), without addition of β-amylase. In this Procedures are 20 ml of a buffered starch solution (prepared by the method described below) in a test tube (diameter mm, length 190 mm) measured and in a water thermostat at a temperature set at 37 ° C. After a few minutes preheated 10 ml of the amylase solution to be tested (or v ml of amylase solution + (10-v) ml of water). The contents of the tube are well mixed and simultaneously you set a stopwatch. At certain time intervals 1 ml of the reaction mixture is diluted 5 ml of a diluted Iodine solution (prepared as described below) admitted, it is shaken and then placed in a comparative Tube is redirected, and the color is using the standard color compared. If the color endpoint in less when it reaches 10 minutes, use one more dilute amylase solution or a smaller volume Amylase.

The colorimeter used is the Hellige Comparator 607 with the glass α-amylase standard (cf. Redfern Methods for determination of α-amylase, Cereal Chemistry 24, 259, (1947)). The α-amylase activity of the sample leaves calculate using the following formula:

wherein
A = α-amylase activity in novo-amylase units per gram
t = time to reach the color end point (minute)
a = weight of the sample in grams
V = volume so that the sample has been diluted (ml)
v = volume of amylase solution used (ml).

The factor "1430" is not strictly constant, but is to some extent depending on the quality of the used Strength. For very accurate determinations, the value should be of the factor can be calculated with the help of one in the trade available standard amylase preparation of known activity.

The above-mentioned "diluted iodine solution" is prepared by adding 1 ml of "storage iodine solution" and 20 g of potassium iodide to 500 ml with water. The "storage iodine solution" is prepared by dissolving 11 g of crystalline iodine and 22 g of potassium iodide in an amount of water equal to 500 ml. The above-mentioned "buffered starch solution" is prepared as follows:
10 g of soluble starch (eg Merck, Amylum solubile, Soluble Starch, Erg. B. 6), calculated as dry matter, is made into a slurry with a little water. The slurry is added to about 200 ml of boiling water. When the starch is completely dissolved, allow the solution to cool, place it in a 1 liter 1 liter flask and make up to the mark with water. Then buffers the starch solution with the buffer solution (prepared by dissolving 9.36 g of NaCl, 69.00 g KH₂PO₄, 4.80 g Na₂HPO₄, 2 H₂O in a 1 liter resulting sufficient amount of water), and finally saturated with the solution Toluene. The pH of the final buffered starch solution should be 5.7. The starch solution must be prepared as fresh as possible; You can store them in the refrigerator, but not longer than 24 hours. In all cases, distilled water is used.

Usually one determines the enzyme activity of proteolytic and amylolytic enzyme preparations from practical Reasons, without the test methods described above perform. For the majority of commercially available containing liquid protease or amylase enzymes Enzyme preparations is the enzyme activity on the part of Manufacturer in Anson units or novo-amylase units (or to these directly proportional units). Alternatively, the activity of a given enzyme preparation be determined analytically in a simple manner, by a method in which the enzyme activity under Standard conditions with any protein or starch Determined substrate and then with the reactivity of reference Enzyme preparations of known activity compared becomes. In such an analytical method can be if desired, express the enzyme reactivity in Shape the optical density of a test solution containing the enzyme preparation and contains the protein or starch substrate, when measured under standard conditions, and then the higher the optical activity, the greater the activity Density is.

Suitable alkaline proteolytic enzymes are, for example the various liquid commercially available Enzyme preparations that are suitable for use in detergent Compositions have been found to be suitable for enzyme Preparations in powdered form may also be used However, they are generally used for the incorporation into liquid cleaning agents according to the invention and detergent compositions are less convenient. To such well-usable liquid enzyme preparations  include those from Novo Industries, Copenhagen, Denmark, distributed products "Alcalase" and "Esperase" as well as from the company Gist-Brocades, Delft, Holland marketed commercial products "Maxatase" and "AZ protease". "Alcalase" is in compositions of the invention especially useful.

For liquid α-amylase Enzyme preparations are for example those of the companies Novo Industries and Gist-Brocades under the trade names "Termamyl" and "Maxamyl" sold products.

It is expedient for liquid washing according to the invention and detergent in combination with water an organic Solvent used as a solution liquid. Preferred organic solvents are, for example lower alkanol having 1 to 4 carbon atoms, the 1 to 3, preferably 1 or 2 hydroxyl groups. Ethanol or a mixture is particularly advantageous Ethanol and isopropanol. Also useful are such mixtures with low monoalcohols, such as propanol and butanol and lower polyols having 2 to 3 carbon atoms, such as ethylene glycol and propylene glycol, although the latter are less preferred. The usage of primary, secondary and tertiary butanol or n-Propanol as a lower alkanol is generally limited to mixtures of these substances with ethanol, with ethanol advantageously make up at least 80 to 90% of such mixtures should. It is very convenient to use ethanol as the only one Use alkanol and organic solvent. If using mixtures of ethanol and isopropanol, it is recommended to use ethanol as the main component, where ethanol is usually 60-90% of the mixture, and preferably in a proportion of 75% (i.e. in a 3: 1 ratio). Of course  other mixtures of different alkanols, such as ethanol and propylene glycol used be, and even in such mixtures should be appropriate Ethanol be the main component.

The detergents and cleaners according to the invention contain one or more surfactants, which are anionic nonionic, cationic, ampholytic and zwitterionic Detergent substances can act. The in practice Synthetic agents used in compositions of the invention Organic surfactants can be any of a variety such well-known and in detail in the treatise Surface Active Agents, Volume II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, be described compounds.

Advantageous nonionic surfactants are usually multiple with low alkoxy groups alkoxylated lipophiles whose hydrophilic-lipophilic balance by addition of a hydrophilic poly-lower alkoxy group to a lipophilic Molecule group has been obtained. Especially useful is in non-ionic surfactant agents of the invention a multiple alkoxylated with lower alkoxy groups higher alkanol, the alkanol being 10 to 18 Contains carbon atoms and the number of moles at low Alkylene oxide (having 2 or 3 carbon atoms) 3 to 12 amounts to. In this group, such substances are preferred in which the higher alkanol is a higher fatty alcohol with 11 or 12 to 15 carbon atoms, the 5 to Contains 8 or 5 to 9 lower alkoxy groups per mole. Advantageously, the lower alkoxy groups are ethoxy groups. However, it may also be desirable for some purposes to use these mixed with propoxy groups, wherein the latter, if they are present, usually a smaller amount (less than 50%)  Form part. Examples of such substances, in which the alkanol component is an alkanol with 12 to 15 carbon atoms and wherein about 7 ethylene oxide groups per mole are those of the company Shell Chemical Company, Inc. manufactured Neodol® products 25-7 and Neodol 23-6.5. The former product is a condensation product of a mixture of higher fatty alcohols with an average of about 12 to 15 carbon atoms, containing about 7 moles of ethylene oxide, and the latter Product is a corresponding mixture of higher Fatty alcohols having 12 to 13 carbon atoms and one Number of an average of 6.5 ethylene oxide groups each Mol. The higher alcohols are primary alcohols.

Further examples of such detergents are Tergitol® 15-S-7 and Tergitol 15-S-9, both from Union Carbide Corporation distributed products containing it are ethoxylated linear secondary alcohols. The former product is a mixed ethoxylated one Product of a linear secondary alcohol with 11 to 15 carbon atoms and 7 moles of ethylene oxide, and the latter product is a similar product, but reacted with 9 moles of ethylene oxide.

Further useful in agents according to the invention higher molecular weight nonionic surfactants, such as for example, the commercial product Neodol 45-11. there these are similar ethylene oxide condensation products higher fatty alcohols in which the fatty alcohol component Has 14 to 15 carbon atoms and the Number of ethylene oxide groups per mole is about 11. Such products are manufactured by Shell Chemical Company manufactured. Other usable nonionic surfactants are those sold under the trade name Plurafac B-26 (BASF  Chemical Company) in which they are reaction products of a higher linear alcohol with a mixture of ethylene and propylene oxides is.

In the preferred present in the inventive compositions Poly-lower alkoxylated higher alcohols achieved the best balance of hydrophilic and lipophilic Molecular groups, if the number of lower alkoxy groups about 40 to 100%, preferably 40 to 60%, of the number at carbon atoms in the higher alcohol. Advantageously, the nonionic detergent is at least 50% of the preferred ethoxylated alkanols, if you have alkanols with higher molecular weights and various other normally liquid nonionic Detergents and surfactants used with, can do this cause the liquid detergent and cleaning agent tends to gel. Consequently one avoids in invention Usually means such substances or limited their quantity, although minor additions to it the cleaning behavior and the like used can be. In terms of which nonionic Surfactants are preferred or less preferably usable, It can be said that the alkyl groups present therein should preferably be linear, although in a small amount Extent even a slight branching can be tolerated can. This applies, for example, if the branching at one beside the carbon atom of the straight Chain seated carbon atom or on two carbon atoms, which removes from the terminal carbon atom sitting and definitely away from the ethoxy chain is present, with the restriction that such branched alkyl radicals not more than 3 carbon atoms are long. Usually the ratio of carbon atoms  low in such a branched configuration rarely, 20% of the total carbon atoms in the alkyl. Similarly, too medially or secondarily linked in the chain ethylene oxide groups be present, although linear alkyls, the are bound to the ethylene oxide chains, are highly preferred. It is believed that these are the optimal combination with regard to cleaning effect, Give degradability and gelling resistance. If medial or secondary links are present, is the Proportion of such alkyls is low, generally it can be less than 20%, however, such as in the aforementioned Tergitols, also be larger. When propylene oxide is present in the lower alkylene oxide chain is usually less than 20%, and preferably less than 10%.

Together with the nonionic detergent, as the main ingredient of synthetic organic detergent in a liquid detergent and cleaner according to the invention is present, one can use an anionic detergent use. Preferred anionic detergent compounds are the higher (10 to 18 or 20 carbon atoms containing) alkylbenzenesulfonate salts, wherein the Contains alkyl group preferably 10 to 15 carbon atoms, and being particularly preferred, straight chain Alkyl radicals having 12 to 18 carbon atoms. It is recommended that such an alkylbenzenesulfonate with a high proportion of 3- (or higher) phenyl isomers and a correspondingly low proportion (usually considerably less than 50%) of 2- (or lower) phenyl isomers; in other words, the benzene ring is advantageous for the most part in the 3-, 4-, 5-, 6- or 7-position with the alkyl group linked, and the proportion of isomers in which  the benzene ring is linked in the 1- or 2-position, is correspondingly low. Typical alkylbenzenesulfonate Surfactants are described in US-PS 33 20 174. If desired, Of course you can also higher branched Alkylbenzolsulfonate use, but these are usually not so beneficial because they are more difficult biological let down.

Other useful anionic detergents are the olefin sulfonate Salts. In general, these contain long-chain Alkenylsulfonates or long-chain hydroxyalkanesulfonates (where the OH group is attached to a carbon, the not directly next to the -SO₃H group bearing C-atom sitting). The olefin sulfonate detergent is in general a mixture of such types of substances in different Amounts, often together with long-chain disulfonates the sulphate sulphonates. Such olefin sulfonates are described in numerous patents, for example in U.S. Patents 2,061,618, 3,409,637, 3,332,880, 3,420,875, 3 428 654, 3 506 580 and in GB-PS 12 129 158. The Number of carbon atoms in the Olefinsulfonat lies usually in the range of 10 to 25, preferably between 10 to 18 or 20. Advantageously, it may be a mixture from mainly C₁₂, C₁₄ and C₁₆ with average 14 carbon atoms or a mixture of mainly C₁₄, C₁₆ and C₁₈ with an average of 16 carbon atoms act.

Another class of useful anionic detergents are the higher paraffin sulphonates. These can be primary Paraffinsulfonate, which they by long-chain reaction α-olefins with bisulfites, e.g. For example, sodium bisulfite obtained be, or may be paraffin sulphonates, along the paraffin chain distributes the sulfonate groups such as the products you go through Reaction of a long-chain paraffin with sulfur dioxide  and oxygen under ultraviolet light and subsequent Neutralization with sodium hydroxide or other obtains suitable base (as for example in the US-PS 2 503 280, 2 507 088, 3 260 741, 3 372 188 and the DE-PS 7 35 096 described). The paraffin sulfonates contain preferably 13 to 17 carbon atoms, and it is usually the monosulfonate. However, you can if desired, also disulfonate, trisulfonates or higher Sulfonates are used. In doing so, typically the di- and polysulfonates together with a corresponding Monosulfonate used, for example as a mixture of mono- and disulfonates in which up to 30% of disulfonate is included. Their hydrocarbon substituent should advantageously be linear, but if desired also a branched chain paraffin sulfonate used although this is not because it is biologically so good is reduced, less recommended.

Other suitable anionic surfactants are sulfated ethoxylated higher fatty alcohols of the formula RO (C₂H₄O) _m SO₃M, wherein R is a fatty alkyl having 10 to 18 or 20 carbon atoms, m 2 to 6 or 8 (preferably a value of about ¹ / ₅ to ½ the number of Carbon atoms in R) and M represents a solubilizing salt-forming cation, such as an alkali, ammonium, lower alkylamino or lower alkanolamino radical, or a higher alkylbenzenesulfonate, the higher alkyl radical of which contains from 10 to 15 carbon atoms. As indicated for the preferred nonionic surfactant, also in the preferred anionic alkoxylated surfactant alkyl is a mixture of chains of different lengths, for example chains of 11, 12, 13, 14 and 15 carbon atoms, or chains of 12 and 13 carbon atoms, over alkylene, which all have one and the same chain length, preferred.

Both for the anionic alkoxylated surfactants as for the nonionic surfactants ethylene oxide is the preferred lower alkylene oxide, and its percentage Proportion is in the polyethoxylated alkanol sulfate preferably 2 to 5 moles of ethylene oxide groups per mole anionic surfactant, with 3 moles being particularly preferred are, especially if the higher alkanol is 11 or Contains 12 to 15 carbon atoms. Um, if the salary on carbon atoms in the alkyl group in the lower Part of the 10 to 18 carbon atoms area located, the desired hydrophilic-lipophilic balance To obtain, you can the ethylene oxide content of the Reduce surfactants to about 2 moles per mole wherever against when the higher alkanol with 16 to 18 carbon atoms in the higher part of this area, the number of ethylene oxide groups to 4 or 5, and in In some cases it can even be increased to 8 or 9. Similarly, the salt-forming cation can be selected be that the best solubility is achieved. Any of these may be suitably soluble serving metal or a rest, but you will in most cases an alkali, for example sodium, or choose ammonium. If lower alkylamine or Alkanolamine groups used to contain the Alkyls or alkanols usually 1 to 4 carbon atoms, and the amines and alkanolamines may be mono-, di- and tri-substituted substances, such as monoethanolamine, diisopropanolamine and trimethylamine.

The poly-lower alkoxy-higher alkanol sulfates can one instead of or in combination with others preferred anionic detergents, such as the higher alkylbenzenesulfonates, use the in accordance with the invention liquid detergents and cleaners available  to supplement nonionic surfactants. A preferred one polyethoxylated alcohol sulfate surfactant is that of available from Shell Chemical Company and under the trade name Neodol 25-3S on the market Product.

Examples of the higher alcohol polyethoxy oxysulfates which can be used in the detergent compositions of the present invention are: the sodium salt of mixed C₁₂ _- C₁₅ normal or primary alkyltriethenoxysulfate, the potassium salt of myristyl triethenoxysulfate, the diethanolamine salt of n-decyldiethene oxysulfate, the ammonium salt of lauryldiethene oxysulfate , the sodium salt of palmityl tetraethoxy oxysulfate, the sodium salt of mixed C _14-15 normal primary alkyl-mixed tri- and tetra-ethenoxy sulfate, the trimethylamine salt of stearyl pentaethenoxy sulfate, and the potassium salt of mixed C _10-18 normal primary alkyl triethenoxysulfate.

Other useful anionic surfactants are the higher ones Acylsarcosinates, e.g. For example, sodium N-lauroylsarcosinate, higher Fatty alcohol sulfates, such as sodium lauryl sulfate and sodium tallow fatty alcohol sulfate, sulfated oils, Sulfates of mono- or diglycerides of higher fatty acids, such as stearin monoglyceride, monosulfate; although of these, the sodium salts of higher alcohol sulfates are not as useful as the polyethoxylated ones Sulfates in the detergents. Furthermore, may be mentioned are aromatic poly (lower alkoxy) ether sulfates, such as the sulfates of condensation products of ethylene oxide and nonylphenol (usually 1 to 20, preferably 2 to 12, oxyethylene groups per molecule have), the polyethoxy-higher alcohol sulfates and the Alkylphenolpolyethoxysulfate, the low Alkoxy substituents (having 1 to 4 carbon atoms,  z. The methoxy group) on the carbon atom, the near which the sulfate group is sitting, such as Monoethylethermonosulfat a long-chain Glycols with adjacent OH groups, eg. B. a mixture of vicinal alkanediols having 16 to 20 carbon atoms in a straight chain, acyl ester of isethionic acid, z. For example, oleyl isethionates, acyl-N-methyltaurides, e.g. For example potassium N methyl lauroyl or oleyl taurides, higher alkyl phenyl Polyethoxysulfonates, higher alkyl phenyl disulfonates, z. Pentadecylphenyl disulfonate, and higher fatty acid soaps, z. B. mixed coconut oil and tallow soaps in one Ratio of 1: 4.

Among the aforementioned types of anionic surfactants For example, the sulfates and sulfonates are generally preferred However, the corresponding organic phosphates can also be used and phosphonates are used when their content Phosphorus is not objectionable. In general are the water-soluble anionic synthetic organic Detergents (including soaps), as indicated above, Salts of alkali cations, such as potassium, Lithium, and especially sodium, though also like previously stated, salts with ammonium and substituted Ammonium cations, for example triethanolamine, triisopropylamine can be used. Given the previously given Examples of water-soluble anionic surfactants should It should be noted that the sodium-potassium-ammonium and Alkanolammonium salts each individually for each surfactant are indicated.

In detergents and cleaners according to the invention used in small amounts ampholytic surfactants, all or part of the anionic surfactants or partially replace the nonionic surfactants such ampholytic surfactants include the higher ones  Fatty carboxylates, phosphates, sulfates or sulfonates which a cationic radical, for example an amino group included, which can be quaternized, for example with a lower alkyl group, or its chain itself at the amino group by condensation with a low Alkylene oxide, for example ethylene oxide, extend. In general, compositions are ampholytic or cationic surfactants, slightly less effective, and they have a greater tendency to gel on standing or to thicken. Therefore, one avoids these frequently. However, if such features are not significant, can in small quantities ampholytic surfactants, such as for example, that of the company Miranol Chemical Company commercialized Miranol C2M or that of the Company General Mills, Inc., under the trade name Deriphat 151 distributed sodium N-coco-β-aminopropionate, to be used. A cationic detergent that is sometimes good is Distearyldimethylammoniumchlorid (it has a fabric softening effect) and the higher fatty amine oxides, such as Bis (2-hydroxyethyl) -octadecylaminoxid.

As the viscosity-controlling agent, which helps to maintain the desired viscosity of the liquid detergent and detergency composition and prevents breakdown at low temperatures, and to lower the content of the lower alkanol solvent, it is preferably a water-soluble formate , Sodium formate is advantageously used, but other alkali formates, for example potassium formate and numerous other water-soluble formates, including formic acid, may also be used. The formic acid is added to the liquid washing and cleaning composition, it dissolves in it, ionized and / or reacted, and it forms substantially the same type of liquid detergent and cleaner, as it results in the addition of alkali formate in salt form , Other formates which can be used are those having water-soluble cations, such as the salt-forming cations for anionic surfactants described above. While it is preferred to use the formate as the viscosity controlling agent herein, it has been found that various salts of dibasic acids can be successfully used, among which the best effective one is the sodium adipate, hereinafter referred to as sodium adipate. Other compounds which are also useful are salts of dibasic acids of the formula (CH₂) _n (COOH) ₂ wherein n is 1 to 6 and in some cases the salts of mono-unsaturated acids of the same chain length and configuration may also be used. However, it is highly recommended to use the saturated aliphatic straight-chain carboxylated end-containing compounds. It is especially preferred to use those in which n is 3 to 5, very advantageously 4, and in which the acid is completely neutralized, although acidic salts can also be used.

Among the useful dibasic acids, both as Mono can be used as a disalts, include Malonic acid, succinic acid, glutaric acid, adipic acid and pimelic acid. An unsaturated dibasic acid, maleic acid may also, at least as a proportion, be used. The acids can be used without prior Neutralization use, but you can also in Use form of their salts, for example as disodium malonate, Monopotassium succinate, ditrethanolamine glutarate, Disodium adipate and monosodium pimelate.  

So that the detergents and optical brighteners, which in the liquid washing and cleaning agent according to the invention Compositions may be present more easily Solutions are often found in the formulas in a small proportion of an alkaline substance or a mixture of such substances is present. Suitable for this Alkaline substances are, for example, mono-, di- and trialkanols, alkylamines, ammonium hydroxides, from preferred alkanolamines, for example trialkanolamines and among these specifically used triethanolamine becomes. The pH of the finished liquid detergents and cleaners Compositions in which such a basic Cloth is usually neutral or light basic. Satisfactory pH ranges are between 7 and 10, preferably about 7.5 to 9 and especially advantageous at 7.5 to 8.5.

The in the liquid detergent and cleaner compositions are used optical fluorescence brightener important components of modern detergents and cleaners, the washed linen and materials a brilliant Appearance so that the laundry is not only clean is, but also looks pure. It is possible, just a single brightener for a special purpose in liquid detergents and cleaners according to the invention but it is generally desirable to that there is a mixture of brighteners, the good lightening effects on cotton fabrics, nylon, Polyester and blended fabrics of such textiles has and which is also pale stable. A good description of such Types of optical brighteners can be found in the article "The Requirements of Present Day Detergent Fluorescent Whitening Agents "by A.E. Siegrist, J. Am. Oil Chemists Soc., January 1978 (Volume 55). This article and the US PS  3 812 041 contain detailed descriptions of a Variety of suitable optical brighteners.

Examples of in liquid inventive and washing Detergents useful brighteners are: Calcofluor 5BM (American Cyanamid); Calcofluor White ALF (American Cyanamid); SOF A-2001 (Ciba); CDW (Hilton Davis); Phorwite RKH; Phorwite BBH and Phorwite BHC (Verona); CSL, powder, Acid (American Cyanamid); FB 766 (Verona); Blancophor PD (GAF); UNPA (Geigy); Tinopal RBS 200 (Geigy). In the Acid or "nonionic" form, the brighteners tend to, in the alcohol portion of the compositions of the invention to go into solution while the salts are more in the Dissolve the water content.

It can be used in the liquid washing and Detergents may still be present adjuvants these additional properties, either more functional or aesthetic type. To such useful Adjuvants include dirt particle suspending and their re-deposit preventing agents, such as Polyvinyl alcohol, sodium carboxymethylcellulose, hydroxypropyl methylcellulose; Thickener, like for example gums, alginates, agar agar; lather such as laurin myristindiethanolamide, Foam destroyers such as silicones, bactericides, such as tribromosalicylanilide, hexachlorophene; dyes; Pigments (water-dispersible); Preservatives; Ultraviolet absorbers; Fabric softening; opacifying agents, such as polystyrene suspensions; and perfumes. Such substances are Of course, selected according to the for the Endprodukt desired properties and after that they are compatible with the other components of the product  are. Other adjuvants that can be used are divalent or trivalent lower alcohols, by the addition of their property, in addition as a solvent to act, reducing the flash point of the product which can act as anti-freezing ingredients ability and compatibility with the particular Product to improve existing solvent system are in the state. Examples of such compounds are as a particularly preferred compound group the low Polyols having 2 to 3 carbon atoms, eg. For example, ethylene glycol, Propylene glycol and glycerol, and with similar good effect For example, the lower alkyl (C₁-C₄) ether derivatives of such Compounds, known as Cellosolves®, can be used. The proportional amounts of such substituents for low Alkanols should be limited, usually up to not more than 20% of the total alcohol in the liquid Detergents and cleaning agents should be limited.

Another category of useful additives are hydrotropes, which serve the solubility of such Components, the inherently limited solubility in water have to improve in the aqueous solution. useful hydrotropes are, for example, alkali metal, ammonium and ethanolamine salts of the following acids: (1) arylsulfonic acids, such as benzenesulfonic acid and C₁-C₃- Alkyl substituted benzenesulfonic acids, e.g. B. toluenesulfonic acid and xylenesulfonic acid; and (2) C₅-C₆ alkyl sulfuric acids, such as hexylsulfuric acid.

The proportional amounts of the various components in liquid detergent and cleaner according to the invention Compositions are important for the formation a uniform product of desired viscosity with an acceptable washing effect when heavily soiled,  at low temperatures or when standing in the open Container not gelled at room temperature.

To increase the solubility of the fluorescence brightener and the other ingredients in the detergent and cleaner Make the composition more soluble, and a clear to produce homogeneous and easily pourable liquid product, should contain 10 to 60% of the total amount of liquid detergent Concentrate nonionic detergent. specially when an anionic detergent in the liquid Product is present, the proportionate amount should be nonionic detergent 20 to 40%, preferably 30 up to 40%, make up and is currently the best about 32%. The proportionate amount of anionic detergent should usually be in the range of 3 to 15%, preferably 4 up to 12% and especially useful 6 to 10% make up and is in the hitherto best recognized recipe 7%. The Ratio of total nonionic detergent to inorganic Detergent is usually 15: 1 to 1: 1, advantageous at 8: 1 to 2: 1 and especially desirable in 5: 1 to 3: 1.

The low alkanol in the liquid washing and cleaning Composition is generally so sufficient Quantity exists that contributes to the different ones Ingredients in the finished product in solution too bring and / or stabilize. The proportional amounts used lower alkanol are usually at about 3 to 15%, preferably 4 to 12% and in particular 4 to 8% and are currently the best effective approach about 5%.  

This used viscosity control agents or a Mixture of such agents should be in an amount of about 0.5 to 5% in the finished liquid detergent and cleaning agent Composition be present, beneficial in in an amount of 0.5 to 3% and especially in one Amount of about 1%.

The percentage of water, the main solvent in liquid detergents and cleaners according to the invention Compositions is usually about 25 to 85% by weight, preferably 35 to 65 wt .-% and particularly useful about 40 to 55 wt .-%, based on the liquid composition. The most preferred recipes have one Water content of 45 to 50 wt .-%.

The content of alkaline additive, such as Triethanolamine, in the liquid composition usually about 0.1 to 5% by weight and preferably 1 to 3% by weight of the composition. The entire proportionate amount optical brightener is usually about 0.05 to 1.5%, preferably about 0.1 to 1% and especially useful about 0.2 to 0.5%.

The liquid detergents and cleaners according to the invention Compositions can be made by simple procedures getting produced. In a typical manufacturing method become the optical brighteners in the monohydric alcohol slurried, then water is combined with a small amount of a base such as triethanolamine, which contributes to the previously suspended material partially dissolve, added to the slurry. If then adding the anionic detergent compound, The remaining brightener dissolves, and you get one clear solution. After that, it will control the viscosity  Agent as acid, acid salt or completely neutralized Salt, preferably as sodium or potassium salt added, and it is stirred until the solution is clear which usually takes about 5 to 10 minutes. In this state, the main detergent ingredient, the nonionic substance, together with a small, adding the pH control controlling amount of acid, and the pH is generally set to such a value, where the proteolytic enzyme used at best is stable. Thereafter, the solution is stirred, and it will be the adjuvants, such as perfume and dye, by which the product the desired properties in the final state receives, added. Then the protease and α-amylase enzyme preparations are added to the solutions and mixed with it, this is the final stage in the Preparation of the liquid washing and Detergent product. If desired, that can the viscosity controlling additives in an earlier Process stage to be incorporated.

The above-described work can be done at room temperature be made; basically can at all temperatures in the range of 20 to 50 ° C worked However, care must be taken that then, if volatiles, such as perfume, are added are, the temperature is so low that is disadvantageous avoidable losses. The obtained Product generally has a pH in the range of 7 to 10 and a density in the range of 0.9 to 1.1, preferably from 0.95 to 1.05. The viscosity of the final product at 24 ° C is in the range of 60 to 150 Centipoises, preferably at about 80 to 140 centipoises, and especially useful at about 115 to 135 centipoises, measured with a Brookfield viscometer at room temperature.  

Inventive liquid detergents and cleaners Compositions are easy to use and have good effect. Compared with powdered detergents For white and coarse laundry, one can have the same cleaning effect with dirty laundry with a smaller one Reach volume of inventive liquid detergent. If, for example, an inventive Uses detergent in a typical preferred recipe, you need for a top-loaded automatic Washing machine with a water volume of 55 to 75 liters only 60 g or 1/4 measuring cup of liquid detergent; and even less (about 1/2) is needed for frontal loaded machines. As a result, the concentration is at inventive liquid detergent in the wash water on the order of about 0.1%. Usually the proportion of liquid detergent is in the wash solution in the range of about 0.0 to 0.3%, preferably at 0.08 to 0.2% and especially useful at 0.01 to 0.15%. The proportional amounts of the various Ingredients in the liquid detergent composition can vary accordingly. equivalent Results are obtained when larger proportions a more diluted formulation, but needed one additional for larger quantities Packaging material, and therefore this is for the Consumers less appropriate. In addition there is at higher diluted products rather the danger that they Freeze in cold climates and subject to them when storing and storing rather the hydrolysis and other chemical changes.  

example 1

At room temperature became a liquid detergent composition (which did not contain enzymes) by mixing the following components in the given proportions Quantities prepared and labeled as composition "A":

Enzyme-containing liquid detergent compositions B-U were added by adding different amounts Protease and α-amylase enzymes to those described above Composition A formulated. The enzyme concentration in each of these detergent compositions is in Table I in wt .-% enzyme content, by weight the composition indicated. As a protease enzyme was a liquid enzyme preparation used under the Trade name "Alcalase" from Novo Industries, Copenhagen, Denmark, and the per gram of enzyme preparation a concentration of Has 2.5 anion units. As α-amylase enzyme was a liquid enzyme preparation used under the trade name "Termamyl" from the company Novo Industries is distributed and a concentration of 120,000 novo-amylase units per gram of liquid Has enzyme preparation.

test method

A total of 6 cotton cloths, 3 of them stained with Rindleberblut and 3 stained with grass, were in each of 4 containers of one of the company U.S.. Testing Company manufactured Tergotometer boiler introduced. It was a series of washing tests performed, respectively a different liquid detergent of the composition A-U used in each container of the Tergotometer has been. The following test conditions were used:

Concentration of liquid detergent | 0.09% Overturning Circulation 100 rpm travel time 10 mins Water temperature approx. 50 ° C Water hardness approx. 150 ppm as calcium carbonate

After washing, the test cloths were in tap water rinsed out and then dried. The percentage Stain removal was measured by pretreatment washing and after washing using a Gardner XL-20 Colorimeters a reflectance value for everyone stained test cloths was read. The value for percentage stain removal (% S.R.) calculated as follows:

where "Rd before washing" means the Rd value after Staining.

From the percent stain removal values, for each 3 test lobes with similar staining was obtained for each liquid examined Detergent composition an average value determined. The results are shown in Table 1. Therein are the% S.R values for each of the tested liquid Detergent composition (compositions A-U) as well the enzyme concentration in these detergent compositions issued.  

Table 1

Comparison for stain removal with enzyme-containing detergent compositions

Percent Stain Removal (S.R.), which, as in Table 1, with which composition A was achieved, represents the S.R. value which, in the absence of Enzymes are achieved in the detergent composition can. If you look at the S.R. values for the Rindleberblut spots looks at and compares these with the S.R. values, that were achieved with the compositions F, K, P and U, all of them contained the compositions F, K, P and U Amylase enzyme, but no protease and were accordingly no inventive detergent, so recognizes that the composition P contained 0.6% by weight of α-amylase, the best S.R. value (47.7%), which was obtained with amylase Enzyme is achievable, namely an increase of about 5.7% compared to the S.R. value of 42% for the enzyme-free Composition A. Similarly, a comparison yields of the S.R. values, which with the compositions B, C, D and E (although all protease enzyme, but no amylase contained) that the 0.8% protease containing composition E achievable with protease enzyme maximum improvement in S.R. value (55.5%) brings that, although an increase of 13.5%, based on the value achieved with the enzyme-free composition A. from 42% S.R.  

The synergistic effect of the combination of protease and amylase enzymes for the removal of proteinaceous Stains can be clearly seen from Table 1. Thus, for example, with the composition G, the 0.2 wt% protease and 0.2 wt% amylase enzymes (indicating a ratio of amylase / protease enzyme activity of 24,000 novo-amylase units per 0.5 Anson units corresponds to) almost the same improvement in S.R. value reach (based on the enzyme-free composition A), the composition containing 0.8% by weight of protease E found. From the economic point of view, the Use of the composition G, according to the invention a Mixture of enzymes, a significant step forward, because the same effect when using greatly reduced Amount of relatively expensive protease enzyme, compared with the composition E, is possible.

The highest value for percent stain removal was achieved with the composition N. This 0.6% by weight Protease and 0.4 wt .-% amylase in combination containing special compositions N gave a percentage increase the S.R. value of 21% in the removal of blood spots, based on the enzyme-free composition A. Here is the Value of 63.3% S.R., which reaches with the composition N. could be significantly higher than the maximum S.R.- Value with the only protease enzyme, but no α-Amylse containing detergent compositions could be achieved. The ratio of amylase protease Enzyme activity in this composition N was 48,000 Novo-amylase units per 1.5 Anson units.

The synergistic effect of protease enzymes and α-amylase enzymes can also be detected if one the S.R. values achieved for the grass stains  were considered. So, for example, with the Composition H containing 0.2% amylase and 0.4% protease Containing a significantly higher S.R. value, when using either the protease enzyme only or just amylase Enzyme as each individual enzyme-containing detergent Compositions could be found.

Claims (13)

An enzyme-containing liquid detergent composition characterized by :

• a) about 5 to 75% by weight of one or more detergent surfactants which may be anionic, nonionic, cationic, ampholytic and / or zwitterionic compounds,
• b) about 25 to 85% water, and
• c) an enzyme mixture consisting essentially of alkaline protease enzyme and α-amylase enzyme, the relative proportions of these enzymes having a ratio of enzyme activities in the mixture of about 4,000 to 80,000 novo-amylase units to α-amylase per Anson unit of protease, and the protease is present in an amount of about 0.25 to 2.5 Anson units per 100 grams of the detergent composition therein.

2. washing and cleaning agent according to claim 1, characterized characterized in that the ratio of enzyme activities in the enzyme mixture present therein approximately 15,000 to 40,000 novo-amylase units on α-amylase each Anson unit makes up protease and the protease in an approximately 0.5 to 2.0 Anson units per 100 g Amount of detergent composition therein is available. 3. Detergent composition after Claim 2, characterized in that therein existing enzyme mixture the ratio of enzyme activities at about 30,000 to 40,000 novo-amylase units α-amylase per Anson unit to protease. 4. Washing and cleaning compositions according to Claim 1, characterized in that therein as Surfactants about 20 to 40 wt .-% of a nonionic, water-soluble C₂ to C₃ alkoxylated C₁₀ to C₁₈- Alkanol detergent and about 4 to 12 wt .-% of a anionic, water-soluble salt of a C₁₀ bis C₁₅-alkylbenzenesulfonate detergent is present and in addition about 3 to 15 wt .-% of a low Alkanols, namely a low monohydric alcohol with 1 to 4 carbon atoms, a low polyol with 2 to 3 carbon atoms or a mixture of these substances.   5. detergent composition according to claim 1, characterized in that in addition about 0.5 to 5 wt .-% of a water-soluble formate salt and / or a dibasic acid of the formula (CH₂) _n (COOH) ₂, wherein n 1 to 6 when the viscosity-controlling agent is present. 6. Enzyme-containing liquid washing and cleaning composition, characterized in that it contains the following constituents:

• a) about 20 to 40 wt .-% of a nonionic detergent compound consisting of a substantially water-soluble C₂ to C₃-alkoxylated C₁₀- to C₁₈- alkanol;
• b) about 4 to 12% by weight of an anionic detergent compound consisting essentially of a water-soluble salt of a C₁₀ to C₁₅ alkylbenzenesulfonate,
• c) about 3 to 15 wt .-% of a low monoalcohol having 1 to 4 carbon atoms and / or a low polyol having 2 to 3 carbon atoms;
• d) about 0.5 to 5% by weight of a water-soluble formate salt as the viscosity-controlling agent;
• e) about 35 to 65% by weight of water; and
• f) an enzyme mixture of substantially alkaline protease enzyme and α-amylase enzyme in a ratio of enzyme activities in the mixture of about 4,000 to 80,000 novo-amylase units to α-amylase per Anson unit to protease resulting relative in proportions, wherein the protease is present in about 0.25 to 2.5 Anson units per 100 grams of detergent composition-yielding amount.

7. Detergents and cleaning compositions according to Claim 6, characterized in that in addition 0.1 to 5 wt .-% of an alkanolamine are included. 8. Detergents and cleaning compositions according to Claim 6, characterized in that the enzymes in the mixture in such relative proportionate amounts that contain the ratio of enzyme activities in the enzyme mixture about 15,000 to 40,000 novo-amylase Units of α-amylase per Anson unit Protease, and the protease in an approximately 0.5 to 2.0 Anson units per 100 g of the detergent Compositions resulting amount is present. 9. Detergent compositions Claim 8, characterized in that the enzymes in the enzyme mixture in such relative proportions Amounts exist that the ratio of enzyme activities about 30,000 to 40,000 novo-amylase units at α-amylase per Anson unit of protease. 10. Detergents and cleaning compositions after Claim 6, characterized in that as nonionic Detergent compound a polyethoxylated C₁₂ to C₁₅ alkanol with 3 to 12 ethylene oxide groups per mole, as an anionic detergent a C₁₂- or C₁₃- Alkylbenzenesulfonate, as low alkanolethanol or a mixture of ethanol and isopropanol, and  as the viscosity-controlling agent, sodium formate available. 11. Washing process in which stained and / or soiled pieces of tissue are washed with an enzyme-containing detergent, characterized in that the enzyme-containing detergent used is an enzyme-containing liquid detergent and cleaner composition which contains the following constituents:

• (a) about 5 to 75% by weight of one or more detergent surfactants, which may be anionic, nonionic, cationic, ampholytic and zwitterionic compounds;
• (b) about 25 to 85% water;
• (c) an enzyme mixture of substantially alkaline protease enzyme and α-amylase enzyme in a ratio of enzyme activities in the mixture of about 4,000 to 80,000 novo-amylase units of α-amylase per Anson unit to protease-yielding relatively proportionate Amounts wherein the protease is present in an amount of about 0.25 to 2.5 Anson units per 100 grams of detergent and cleaner compositions.

12. The method according to claim 11, characterized that such a detergent is used, which contains an enzyme mixture in which the ratio of Enzyme activities about 15,000 to 40,000 novo-amylase Units of α-amylase per Anson unit to protease and wherein the protease is in an approximately 0.5 up to 2.0 Anson units per 100 g of washing and cleaning agent Composition resulting amount present is.   13. The method according to claim 11, characterized in that a liquid detergent and cleaning composition is used, which consists essentially of the following components:

• (A) about 20 to 40 wt .-% of a nonionic surfactant compound of a water-soluble C₂ to C₃ alkoxylated C₁₀- to C₁₈ alkanol,
• (b) about 4 to 12% by weight of an anionic surfactant compound of a water-soluble salt of a C₁₀ to C₁₅ alkylbenzenesulfonate;
• (c) about 3 to 15% by weight of a lower monoalcohol having 1 to 4 carbon atoms and / or a lower polyol having 2 to 3 carbon atoms;
• (d) about 0.5 to 5% by weight of a water-soluble formate salt as the viscosity-controlling agent;
• (e) about 35 to 65% by weight of water; and
• (f) an enzyme mixture of alkaline protease enzyme and α-amylase enzyme is a ratio of the corresponding enzyme activities in the mixture of about 4,000 to 80,000 novo-amylase units to α-amylase per Anson unit of protease-producing relative proportionate amounts wherein the protease is present in an amount of about 0.25 to 2.5 Anson units per 100 grams of the detergent and cleaner compositions therein.