DE3344097A1 - ENZYME-CONTAINING LIQUID DETERGENT AND CLEANING AGENT - Google Patents

Description

description

The invention relates to an enzyme-containing (- liquid detergent composition, which is both can be used for soaking and prewashing as well as detergent for the main wash cycle, and concerns a such an agent, the mixture of the enzymes protease and amylase in certain proportions set in this way contains that a particularly effective removal of dirt and stains during the washing process is achieved.

There are already enzymes containing liquid detergent compositions known and noticed. This is the main reason why enzymes are used in detergent compositions incorporated because one is the ability of proteolytic and amylolytic enzymes to move of protein and starch substances that are in

and find it on soiled fabrics, would like to make effective use of so that stains, such as sauce stains, Blood stains, chocolate stains and the like can be removed more easily during the washing process.

However, the use of enzymatic substances, especially 25

proteolytic enzymes that are suitable for detergent purposes, comparatively expensive. Even if only they are present in relatively small amounts, they are generally the most expensive ingredients in a typical commercial liquid detergent and cleaning agent. In addition, you usually have to have one Provide excess of enzymes for a certain detergent composition, because as a result of the known Instability of enzymes in aqueous compositions, such an excess of enzyme is required in the formulation usually in order to anticipate the loss of enzyme activity

to encounter during longer storage periods. This with the The disadvantages associated with the use of enzymes in liquid detergents and cleaning agents have hitherto been a general one widespread, commercial use of such compositions stood in the way.

Detergent compositions containing mixtures of enzymes, e.g., proteases and amylases, are several has been described. For example, US Pat. No. 3,630,930 describes a granular detergent which contains about 0.5 to 20% of enzyme carrier granules, and the enzyme granules consist of about 0.001 to 10% of the mixture of protease and amylase enzymes in a weight ratio of protease to amylase from 50: 1 to 1: 5. Ih the GB-PS 1 240 058 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 contain amylase, the amylase in an amount

from 0.0003 to 3% by weight, based on the detergent add-ons

composition, is present in it. U.S. Patent 3,931,034

relates to a washing and cleaning agent granulate., the alkaline protease and <a £> -amylase enzymes in a _{mixture resulting in an activity ratio of 100,000 to 400,000 Novo-Amylase-P 5} units of amylase per Anson units of protease contains.

Accordingly, it is the use of enzyme mixtures in granulated detergents and cleaning agents generally stated in the patent literature, however the enzyme mixtures as such are in most cases described so broadly that they are e.g. Mixtures with include, in which the percentage of protease can vary over 5 orders of magnitude (GB-

PS 1 240 058), or in which the percentage of

""l.:"OO 33U097 9

Amylase can vary over 5 orders of magnitude (US Pat. No. 3,630,930). This encourages the expert in the assumption that the more effective the stain-removing effect, the greater, the more extensive it is

Ranges that is amount of enzyme used. Above 5

In addition, the aforementioned patents relate in the same way as US Pat. No. 3,931,034 specifically to such detergents and cleaning agents in granulated form and thus give the person skilled in the art no indication of the use of enzyme mixtures in liquid compositions.

The present invention relates to an enzyme-containing liquid detergent and cleaning agent composition. According to the invention, this consists of:

(a) About 5 to 75% by weight of one or more surfactants, namely anionic, nonionic, cationic, ampholytic or zwitterionic surfactant or detergent substances;
(b) about 25 to 85% water; and

(c) an enzyme mixture consisting essentially of an alkaline protease enzyme and a cLrhmy lase enzyme, which has these two enzymes in a ratio of enzyme activities of about 4000 to 80,000 Novo-Amylase units anöi-Amylase per Anson unit Contains relative amounts yielding protease, the protease being present in such an amount that there are about 0.25 to 2.5 Anson units per 100 g of total composition.

The invention also relates to a washing method for cleaning stained and / or soiled materials, which is characterized in that one these materials come into contact with an aqueous solution of the liquid detergent and cleaning agent according to the invention brings.

It has surprisingly been found that the amount of alkaline protease enzyme usually required for removal The amount of protein staining required can be reduced quite significantly when you combine this enzyme with a 5 specified for the agent according to the invention

Amylase Enzyme Applied. According to the invention, this is obtained a detergent and cleaning agent composition that is equivalent to the previously known agents or has improved soil removal ability, but significantly less than that has a complex recipe. Different from those present in the previously known detergent compositions Enzyme mixtures in which proteases and amylases are present in a very wide range combined in terms of quantity found that the detergents and cleaning agents according to the invention envisaged enzyme mixtures have a characteristic synergistic effect between protease and Amylase have and exclusively these mixtures, which have the specified narrowly defined activity ratio, include.

The activities of the alkaline protease enzymes and ££ - amylase enzymes are given in Anson units for protease or novo amylase units for amylase. The person skilled in the art usually uses these units for 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 contain enzyme mixtures, the alkaline protease and ^ c-amylase in such Contain amounts which contain 10,000 to 50,000 Novo-Amylase units of fl £ -amylase per Anson unit of protease are, more advantageous still the activity ratio between

between about 15,000 and 40000, and particularly desirably such a ratio is between about 30,000 and 40,000 is.

The amount of in a liquid laundry detergent according to the invention and detergent composition present enzyme mixture is to some extent dependent on the amount of compositions to be added to the washing liquor for detergents and cleaning agents that are intended are for use in domestic automatic washing machines at concentrations of about 0.15% in the washing solution such an amount of mixture is appropriate that about 0.25 to 2.5 Anson units of protease each 100 g detergent and cleaning agent composition, especially

advantageously in 0.5 to 2.0 and especially desirably about 1.5 Anson units per 100 g of composition is introduced.

As previously stated, the activity is alkaline Protease enzyme measured in Anson units. The Anson 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 79-89 (1939). One can choose to measure the proteolytic Activity also of the modified Anson hemoglobin method serve. The modified method is described in the article "Alkali-Resistant Enzyme for Detergents", S.R. Green, Soap and Chemical Specialties, pp. 86, 88, 90, 94 and 133, May 1968. Used in this method one in principle the alkaline protease enzyme in the way that in a buffered aqueous medium. At a selected pH value under standard conditions a de-

natured hemaglobin substrate is consumed and one determines the amount of material consumed by a color test with phenolic reagent.

The activity of the ^ lC-amylase enzyme is, as said before, 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 the addition of β-amylase. With this one Procedure, 20 ml of a buffered starch solution (prepared using the method described below) measured into a test tube (diameter mm, length 190 mm) and placed in a water thermostat at a temperature set of 37. After a few minutes of preheating, 10 ml of the amylase solution to be tested are added (or ν ml amylase solution + (10-v) ml water) added. The contents of the tube are mixed well and a stopwatch is started at the same time. At certain time intervals add 1 ml of the reaction mixture to 5 ml of a dilute iodine solution (prepared as described below) added, shaken and then transferred to a comparison tube, and the color becomes the standard color compared. If the color end point is reached in less than 10 minutes, a stronger one is used diluted amylase solution or a smaller volume of amylase solution.

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

. 1430 χ V.

A = where

t χ a χ ν

A = Λ-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 to which the sample has been diluted (ml) v = volume of amylase solution used (ml).

The factor "1430" is not strictly contant, but is to some extent dependent on the quality of the starch used. For very precise determinations, the value should be of the factor can be calculated using a standard commercially available amylase preparation of known activity.

The above-mentioned "dilute iodine solution" is made in the manner

prepared that 1 ml of "storage iodine solution" and 20 g of potassium iodide are made up to 500 ml with water. the Stock iodine solution "is obtained by dissolving 11 g of crystalline iodine and 22 g of potassium iodide in such an amount of water as

that result in 500 ml, prepared. The above-mentioned 20

"Buffered starch solution" is prepared as follows:

10. g of soluble starch (e.g. Merck, Amylum solubile, Soluble Starch, Erg. B.6), calculated as the dry matter, are mixed with a little water to form a slurry. The slurry is added to about 200 ml of boiling water. When the starch is completely dissolved, the solution is allowed to cool, poured into a 1 liter flask and made up to the mark with water. Then the starch solution is buffered with the buffer solution (prepared by dissolving 9.36 g NaCl, 69.00 g KH ₂ PO., 4.80 g Na ₃ HPO ₄ , 2 H ₃ O in a 1 liter sufficient amount of water) and finally the solution is saturated with toluene. The pH of the finished, buffered starch solution should be 5.7. The starch solution must be prepared as freshly as possible; they can be kept in the refrigerator, but no longer than

24 hours. Distilled water is used in all cases.

Usually one determines the enzyme activity of proteolytic and amylolytic enzyme preparations from practical means Reasons for not performing the test procedures described above. For the majority of those commercially available liquid enzyme preparations containing protease or amylase enzymes is the enzyme activity on the part of the Manufactured in Anson units or Novo-Amylase units (or units directly proportional to these). Alternatively, the activity of a given enzyme preparation can be determined analytically in a simple manner, by a process in which enzyme activity under standard conditions with any protein or starch substrate determined and then compared with the reactivity of reference enzyme preparations of known activity will. In such an analytical method, the enzyme reactivity can, if desired, be expressed in Form of the optical density of a test solution containing the enzyme preparation and the protein or starch substrate, when measured under standard conditions, and then the higher the optical, the greater the activity Density is.

Suitable alkaline proteolytic enzymes are, for example, the various liquid commercially available Enzyme preparations which have been found suitable for use in detergent compositions, enzyme preparations in powdered form can also be used, but are generally said to be for the incorporation into liquid cleaning and detergent compositions according to the invention is less convenient. to such useful liquid enzyme preparations

belong to the company Novo Industries, Copenhagen, Denmark, distributed products "Alcalase" and "Esperase" as well as the commercial products "Maxatase" and "AZ-Protease" sold by Gist-Brocades, DeIft, Holland. "Alcalase" is particularly useful in compositions according to the invention.

Liquid amylase enzyme preparations suitable for purposes according to the invention 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 laundry detergents according to the invention and cleaning agents in combination with water an organic

Niche solvent used as the dissolving liquid.

Preferred organic solvents are, for example lower alkanols with 1 to 4 carbon atoms which have 1 to 3, preferably 1 or 2, hydroxyl groups.

Ethanol or a mixture of 20 is particularly advantageous

Ethanol and isopropanol. Such mixtures can also be used with lower monoalcohols, such as propanol and butanol and lower polyols with 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 lower alkanol is generally limited on mixtures of these substances with ethanol, ethanol advantageously making up at least 80 to 90% of such mixtures should. It is very useful to use ethanol as the only alkanol and organic solvent. if if mixtures of ethanol and isopropanol are used, it is advisable to use ethanol as the main component, with ethanol usually making up 60 to 90% of the mixture, and preferably at a level of 75% (i.e. in a 3:! ratio). Of course

Other mixtures of the various alkanols, such as ethanol and propylene glycol, can be used and in such mixtures, too, ethanol should expediently be the main component.

The detergents and cleaning agents according to the invention contain one or more surfactants, which are anionic ·> may act nonionic, cationic, ampholytic and zwitterionic detergent substances. In practice Synthetic organic surfactants used in compositions of the invention can be any of a variety such well-known and detailed in the treatise Surface Active Agents, Volume II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers,

" ¹ ^ be the connections described.

Advantageous nonionic surfactants are usually lipophiles alkoxylated several times with lower alkoxy groups, their hydrophilic-lipophilic balance by adding one

hydrophilic poly-lower alkoxy group to a lipophilic Molecular group has been obtained. It is particularly useful as a nonionic surfactant in agents according to the invention a higher alkanol which is multiply alkoxylated with lower alkoxy groups is present, the alkanol being 10 to 18

Contains carbon atoms and the number of moles of low Alkylene oxide (with 2 or 3 carbon atoms) 3 to 12 is. In this group, those substances are preferred in which the higher alkanol is a higher fatty alcohol of 11 or 12 to 15 carbon atoms containing 5 to 8 or 5 to 9 lower alkoxy groups per mole. The lower alkoxy groups are advantageous ethoxy groups. However, for some purposes it may also be desirable to use these mixed with propoxy groups, the latter usually being used if they are present one present in a smaller amount (less than 50%)

Form part. Examples of those substances in which the alkanol component is an alkanol with 12 to Is 15 carbon atoms and wherein about 7 ethylene oxide groups per mole are present, the products manufactured by Shell Chemical Company, Inc. are Neodor ** ' 25-7 and Neodol 23-6.5. The first-mentioned product is a condensation product of a mixture of higher fatty alcohols having an average of about 12 to 15 carbon atoms, containing about 7 moles of ethylene oxide, and the latter The product is a corresponding mixture of higher fatty alcohols with 12 to 13 carbon atoms and one Number of an average of 6.5 ethylene oxide groups per mole. The higher alcohols are primary alcohols. / *.

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

Furthermore, nonionic surfactants with a higher molecular weight, such as for example the commercial product Neodol 45-11. These are similar ethylene oxide condensation

products of 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 made by Shell Chemical Company. Other usable non-ionic surfactants are those under the trade name Plurafac B-26 (BASF

Chemical Company) which are reaction products of a higher linear alcohol acts with a mixture of ethylene and propylene oxides.

With those preferably present in the agents according to the invention Poly-low alkoxylated higher alcohols achieve the best balance of hydrophilic and lipophilic Molecular groups when the number of lower alkoxy groups "Ό about 40 to 100%, preferably 40 to 60% of the number of carbon atoms in the higher alcohol. The nonionic detergent advantageously exists at least 50% from the preferred ethoxylated alkanols,

if you use alkanols with higher molecular weights and 15

using various other normally liquid nonionic detergents and surfactants can do this lead that the liquid detergent and cleaning agent tends to gel. Accordingly, one avoids in the invention Usually means such substances or limits their amount, albeit small additions thereof for promotion the cleaning behavior and the like can also be used. With regard to which non-ionic Surfactants are preferred or can be used less preferably, it can be said that the alkyl groups present therein should preferably be linear, although slight branching will also be tolerated to a minor extent can. This applies, for example, if the branching is on a straight carbon atom next to the terminal one

Chain seated carbon atom or on two carbon atoms, which are located away from the terminal carbon atom and in any case at a distance from the ethoxy chain exists, with the caveat that such

branched alkyl radicals no more than 3 carbon atoms 35

are long. Usually the ratio of carbon

atoms in such a branched configuration are low rarely make up 20% of the total carbon atoms in the alkyl. Similarly, you can too

Ethylene oxide-5 bound medially or secondarily in the chain

groups are present, although linear alkyls that are fully bonded to the ethylene oxide chains, are highly preferred. It is assumed that this is the optimal combination in terms of cleaning action, bio-

- _{10 give} degradability and gel resistance. If medial or secondary links are present, the proportion of such alkyls is only small, in general it is less than 20%, but can also be greater, as is the case with the aforementioned tergitols, for example.

If propylene oxide is present in the lower alkylene oxide chain, this should usually also be less than 20% / and preferably make up less than 10%.

Along with the non-ionic detergent that is the main ingredient of synthetic organic detergent in a liquid washing and cleaning agent according to the invention is present, an anionic detergent can be used. Preferred anionic detergent compounds are the higher (10 to 18 or 20 carbon atoms

containing) alkylbenzenesulfonate salts, in which the -Alkyl group preferably contains 10 to 15 carbon atoms, and it is particularly preferred to be straight-chain Is alkyl radicals with 12 to 18 carbon atoms.

It is recommended to use such an alkylbenzenesulfonate 30th

a high proportion of 3- (or higher) phenyl isomers and a correspondingly low proportion (usually well below 50%) of 2- (or lower) phenyl isomers; in other words, the benzene ring is advantageously largely 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 alkyl benzene sulfonate surfactants are described in U.S. Patent 3,320,174. If so desired you can of course also use more highly branched alkylbenzenesulfonates, but these are usually not as beneficial because they are more difficult to biodegrade.

Other useful anionic detergents are the olefin sulfonate salts. In general, these contain long-chain alkenyl sulfonates or long-chain hydroxyalkanesulfonates (the OH group being attached to a carbon that is not directly next to the carbon atom bearing the -SO ^ H group). The olefin sulfonate detergent is generally a mixture of such types of substances in varying amounts, often together with long chain disulfonates of the sulfate sulfonates. Such olefin sulfonates are described in numerous patents, for example in US Pat. No. 2,061,618, 3,409,637, 3,332,880, 3,420,875, 3,428,654 3,506,580 and in British Pat the olefin sulfonate is usually in the range from 10 to 25, preferably between 10 to 18 or 20. It can advantageously be a mixture of mainly C ₁₀ , C ₁ . and C ₁ , with an average of 12 14 16

14 carbon atoms or a mixture of mainly C _1. , C _{1 c} and C ₁₀ with an average of 16 carbon-14 Ib Io

act atoms.

Another class of useful anionic detergents are the higher paraffin sulfonates. These can be primary Be paraffin sulfonates, which make them long-chain by reaction ^ Olefins with bisulfites, e.g. sodium bisulfite, are obtained or it can be paraffin sulfonates, along the paraffin chain distributes the sulfonate groups such as the products obtained by reacting a long-chain paraffin with sulfur dioxide

• «a

and oxygen under ultraviolet light and subsequent neutralization with sodium hydroxide or another suitable base is obtained (as, for example, in US Pat. Nos. 2,503,280, 2,507,088, 3,260,741, 3,372,188 and US Pat DE-PS 735 096 described). The paraffin sulfonates contain preferably 13 to 17 carbon atoms and it is usually the monosulfonate. However, you can if desired also disulfonate, trisulfonate or higher Sulphonates can be used. Typically

the di- and polysulfonates together with a corresponding one Monosulfonate used, for example, as a mixture of mono- and disulfonates in which up to 30% of disulfonate is included. Their hydrocarbon substituent -j 5 should advantageously be linear, but it can, if desired A branched-chain paraffin sulfonate can also be used, although this is because it is not so good biologically is less recommended.

Other suitable anionic surfactants are sulfated ethoxylated higher fatty alcohols of the formula RO (C ₂ H ₄ O) SO_M, where R is a fatty alkyl with 10 to 18 or 20 carbon atoms, m 2 to 6 or 8 (preferably a value of about 1/5 to 1/2 the number of carbon atoms in R) and M

² ^ a solubilizing salt-forming cation, such as an alkali, ammonium, a lower alkylamino or lower alkanolamino radical, or a higher alkylbenzenesulfonate whose higher alkyl radical contains 10 to 15 carbon atoms, mean. As for the preferred one

Nonionic surfactant indicated is a mixture as alkyl in the preferred anionic alkoxylated surfactant as well of chains of different lengths, for example chains with 11, 12, 13, 14 and 15 carbon atoms, or chains with 12 and 13 carbon atoms, preferred over alkylene, which all have one and the same chain length.

Ul '.! .. ::! ■ Ov ^: 334a097

Ethylene oxide is that for both the anionic alkoxylated surfactants and the nonionic surfactants preferred lower alkylene oxide, and its percentage is in the polyethoxylated alkanol sulfate preferably 2 to 5 moles of ethylene oxide groups per mole of anionic surfactant, 3 moles being particularly preferred are, especially when the higher alkanol contains 11 or 12 to 15 carbon atoms. Um if the salary of carbon atoms in the alkyl group in the lower

"Ό Part of the range containing 10 to 18 carbon atoms is located to obtain the desired hydrophilic-lipophilic balance, one can adjust the ethylene oxide content of the Reduce surfactant to about 2 moles per mole, as opposed to when the higher alkanol having 16 to 18 carbon atoms in the higher part of this range / the number of ethylene oxide groups ranks at 4 or 5, and in In some cases it can even be increased to 8 or 9. Similarly, the salt-forming cation can be so selected that the best solubility is achieved.

Any suitably solubilizing metal or residue can be used, but will in most cases choose an alkali such as sodium or ammonium. Unless low alkylamine or Alkanolamine groups are used, the alkyls or alkanols usually contain 1 to 4 carbon atoms, and the amines and alkanolamines can be mono-, di- and tri-substituted substances, such as monoethanolamine, diisopropanolamine and trimethylamine.

The poly-lower alkoxy-higher alkanol sulfates can instead of or in combination with other preferred anionic detergents, such as, for example 35

higher alkylbenzenesulfonates, use those in the invention liquid detergents and cleaning agents

to supplement existing nonionic surfactants. A preferred polyethoxylated alcohol sulfate surfactant is that of available from Shell Chemical Company and marketed under the trade name Neodol 25-3S Product.

Examples of the higher alcohol polyethenoxysulfates that can be used in the detergent and cleaning agent compositions _{according to the invention are: The sodium salt of mixed Ci 2-} Tc normal or primary alkyltriethenoxysulfate, the potassium salt of myristyltriethenoxysulfate, the diethanolamine salt of n-decyldiethenoxysulfate, the Ammonium salt of lauryl diethenoxy sulfate, the sodium salt of palmityl tetraetheneoxy sulfate, the sodium salt

"* 5 of mixed C,.. _ Normal primary alkyl mixed tri- and tetra-ethenoxy sulfate, the trimethylamine salt of stearyl pentaethene oxysulfate and the potassium salt of mixed C-in-ia normal primary alkyl triethenoxy sulfate

Other useful anionic surfactants are the higher ones Acyl sarcosinates, e.g. sodium N-lauroyl sarcosinate, higher Fatty alcohol sulfates, such as sodium lauryl sulfate and sodium tallow alcohol sulfate, sulfated oils, Sulphates of mono- or diglycerides of higher fatty acids, such as, for example, stearic monoglyceride, monosulphate; although of these, the sodium salts of higher alcohol sulfates are not as useful as the polyethoxylated ones Sulphates in detergents. Aromatic poly (lower alkenoxy) ether sulfates can also be mentioned, such as the sulfates of condensation products of ethylene oxide and nonylphenol (which are usually 1 to 20, preferably 2 to 12, oxyethylene groups per molecule), the polyethoxy-higher alcohol sulfates and the alkylphenol polyethoxy sulfates, which have a low Alkoxy substituents (with 1 to 4 carbon atoms,

e.g. the methoxy group) on the carbon atom that close to which the sulfate group is located, such as, for example, monoethyl ether monosulfate of a long-chain Glycol with adjacent OH groups, e.g. a mixture

_ of vicinal alkanediols with 16 to 20 carbon atoms 5

in a straight chain, acyl ester of isethionic acid, e.g. oleyl isethionate, acyl-N-methyltauride, e.g. potassium-N-methyllauroyl- or oleyltauride, higher alkyl phenyl polyethoxysulfonates, higher alkyl phenyl disulfonates, e.g. pentadecylphenyl disulfonate, and higher fatty acid soaps, e.g. mixed coconut oil and tallow soaps in a ratio of 1: 4.

Among the aforementioned types of anionic surfactants ^ ^5, the sulphates and sulphonates are generally preferred, but it can also be used the corresponding organic phosphates and phosphonates, if the content thereof is not objectionable to phosphorus. In general, the water soluble anionics are synthetic organic

Detergents (including soaps) as indicated above, salts of alkali cations such as potassium, Lithium and especially sodium, although also, as mentioned above, salts with ammonium and substituted ones Ammonium cations, for example triethanolamine, triisopropylamine, can be used. With the previously given Examples of water-soluble anionic surfactants should be noted that the sodium-potassium-ammonium and Alkanolammonium salts individually for each surfactant 3Q are indicated.

In detergents and cleaning agents according to the invention can small amounts of ampholytic surfactants are used, to completely or partially replace the anionic surfactants or partially replace the nonionic surfactants such ampholytic surfactants include the higher ones

Fatty carboxylates, phosphates, sulfates or sulfonates that contain a cationic radical, for example an amino group which can be quaternized, for example with a lower alkyl group, or whose chain can be

on the amino group by condensation with a low 5

Alkylene oxide, for example ethylene oxide, can be extended.

In general, compositions containing ampholytic or cationic surfactants are somewhat less effective, and they have a greater tendency to

^ q lieren or thicken. Therefore, one often avoids them.

However, if such properties are not important, Ampholytic surfactants such as those from Miranol Chemical Company can be used in small amounts Marketed Miranol C2M or that by General Mills, Inc. under the trade designation Deriphat 151 sold sodium N-coco-ß-amine propionate, to be used. A cationic detergent that is sometimes useful is distearyldimethylammonium chloride (it has a softening effect on the fabric)

and the higher fatty amine oxides such as bis (2-hydroxyethyl) octadecyl amine oxide.

As a viscosity control agent that helps ensure the desired viscosity of the liquid detergent and Maintain detergent composition and prevent gelation at low temperatures, and that it allows the level of the lower alkanol solvent to be reduced, it is preferably a water-soluble one Formate. Sodium formate is advantageously used, however, other alkali metal formates, for example Potassium formate and numerous other water-soluble formates, including formic acid, can be used. The formic acid if one adds to the liquid washing and cleaning composition, it dissolves in it, ionizes and / or reacts and essentially the same thing forms

Type of liquid detergent and cleaning agent that results from the addition of alkali formate in salt form. Other formates that can be used are

those with water-soluble cations, such as those previously described-5

benign salt-forming cations for anionic surfactants. Albeit used as a viscosity control agent preferably the formate can be used, as has been found, various salts of dibasic acids with

..Q success can be used, of which apparently the most effective is sodium adipate, hereinafter referred to as sodium adipate. Further compounds which can also be used are salts of dibasic acids of the formula (CH ₂ ) (COOH) -, in which η is 1 to 6, and in some cases the salts of mono-unsaturated acids of the same chain length and configuration can also be used. However, it is very advisable to use the saturated aliphatic straight-chain compounds having carboxylated end groups. Particular preference is given to using those in which η is 3 to 5, very advantageously 4, and in which the acid is completely neutralized, although acid salts can also be used.

Among the useful dibasic acids, both as

Mono- as can be used as disalts include malonic acid, succinic acid, glutaric acid, adipic acid and pimelic acid. An unsaturated dibasic acid, maleic acid, can also, at least as a part, can be used. The acids can be used without prior neutralization, but they can also be used in Use the form of their salts, for example as disodium malonate, monopotassium succinate, ditriethanolamine glutarate, Disodium adipate and monosodium pimelate.

So that the detergents and optical brighteners that are used in the liquid detergent and cleaning agent compositions according to the invention can be present, can be brought into solutions more easily, is often in the formulations an alkaline substance or a mixture of such substances is present in small proportions. Suitable for it alkaline substances are, for example, mono-, di- and trialkanolamines, alkylamines, ammonium hydroxides, from those preferred alkanolamines, for example trialkanolamines and, among these, especially triethanolamine will. The pH of the finished liquid detergent and cleaning agent compositions, containing such a basic substance is usually neutral or light basic. Satisfactory pH ranges are between 7

and 10, preferably from about 7.5 to 9 and particularly advantageously from 7.5 to 8.5.

The ones in the liquid detergent and cleaning agent compositions fluorescent optical brighteners used 20th

important components of modern detergents and cleaning agents, which give the washed laundry and the materials a shining light Appearance so that the laundry is not only clean, but also looks clean. It is possible

pe only a single brightener for a special purpose to be provided in liquid detergents and cleaning agents according to the invention, but it is generally desirable that there is a mixture of brighteners that have good brightening effects on cotton fabrics, nylon, Has polyester and blended fabrics of such textiles and which is also stable to bleach. 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 U.S. PS

334-097

3,812,041 contain detailed descriptions of a variety of suitable optical brighteners.

Examples of liquid detergents and detergents according to the invention

Brighteners that can be used for cleaning agents are: Calcofluor 5

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 be to go in the alcohol portion of the agents according to the invention in solution, while the salts tend to be in the Dissolve the water content.

It can be used in the inventive liquid washing and Cleaning products still contain adjuvants that have these additional properties, either more functional or aesthetic. To such useful ones

Adjuvants include dirt particle suspending and redeposition preventing agents, such as Polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxypropylmethyl cellulose; Thickeners, like

for example gums, alginates, agar agar; Foam Verification 25

serer, such as lauric myristine diethanolamide, foam destroyer, such as silicones, bactericides, such as tribromosalicylanilide, hexachlorophene; Dyes; Pigments (water dispersible); Preservatives; Ultraviolet absorbers; Fabric softener; opacifying agents such as polystyrene suspensions; and perfumes. Such substances are of course selected according to the for the End product desired properties and then that they are contracted with the remaining ingredients of the agent

3 34 A

are. Other adjuvants that can be used are dihydric or trihydric lower alcohols, due to the fact that, in addition to their ability to also act as a solvent, the flash point of the product is reduced that can act as anti-freezing ingredients are able to improve the compatibility with the solvent system present in the specific product are able to. Examples of such compounds are, as a particularly preferred group of compounds, the lower ones

Polyols with 2 to 3 carbon atoms, e.g. ethylene glycol, Propylene glycol and glycerine, and the lower alkyl (C 1 -C.) Ether derivatives of these can have a similarly good effect Compounds known as cellosolves can be used. The proportional amounts of such substituents for low

Alkanols should be limited, usually up to no more than 20% of the total alcohol in the liquid Detergents and cleaning agents are limited.

Another category of useful additives are hydrotropes, which serve to improve the solubility in the aqueous solution of such components, which have limited solubility in water. Useful hydrotropes are, for example, alkali, ammonium and ethanolamine salts of the following acids: (1) arylsulfonic acids, such as, for example, benzenesulfonic acid and C.sub.1 -C.sub.1 -alkyl-substituted benzenesulfonic acids, for example toluenesulfonic acid and xylenesulfonic acid; and (2) C_-C _fi -alkylsulfur-

acids such as hexylsulfuric acid. 30th

The proportional amounts of the various components in liquid detergent and cleaning agent compositions according to the invention are important for the formation of a uniform product of the desired viscosity with an acceptable washing effect on heavy soiling,

that does not gel at low temperatures or when left in an open container at room temperature.

To determine the solubility of the fluorescent brighteners and the

other ingredients in the detergent and cleaning agent composition to make it more soluble and to produce a clear, homogeneous and easily pourable liquid product, 10 to 60% of the total amount of liquid detergent concentrate should be nonionic detergent. Special then, if an anionic detergent is present in the liquid product, the proportionate amount should be nonionic detergent make up 20 to 40%, preferably 30 to 40% and is currently the best "15 about 32%. The proportionate amount of anionic detergent should usually be in the range of 3 to 15%, preferably up to 12% and particularly expediently 6 to 10% and amounts to 7% in the recipe that has so far been recognized as the best. That Ratio of total nonionic detergent to inorganic

chemical detergent is usually 15: 1 to 1: 1, advantageously at 8: 1 to 2: 1 and particularly desirable at 5: 1 to 3: 1.

The lower alkanol in the liquid detergent and cleaning composition is generally present in sufficient quantity to help serve the various Bringing constituents in the finished product into solution and / or stabilizing. The proportional quantities the lower alkanol used is usually about 3 to 15%, preferably 4 to 12% and in particular 4 to 8% and is around 5% for the currently most effective approach.

i &: "- ·:: ^{f / O '..:} 33A4097 3-f

The viscosity control agent used, 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, advantageously 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 detergent and cleaning agent compositions according to the invention is usually about 25 to 85% by weight, preferably 35 to 65% by weight, and particularly useful about 40 to 55% by weight, based on the liquid composition. The most preferred recipes have one Water content of 45 to 50% by weight.

The content of an alkaline additive such as triethanolamine in the liquid composition is usually about 0.1 to 5%, 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 particularly useful about 0.2 to 0.5%.

The liquid washing and cleaning agent compositions according to the invention can be produced using simple working methods. In a typical manufacturing method the optical brighteners are suspended in the monohydric alcohol, then water is mixed with one small amount of a base, such as triethanolamine, which will help maintain the previously suspended material partially to dissolve added to the slurry. if the anionic detergent compound is then added,

the rest of the brightener dissolves, and you get a 35

clear solution. After that, it becomes the viscosity control

- * "3 &'-

Agent as acid, acid salt or completely neutralized salt, preferably as sodium or potassium salt " and stir until the solution becomes clear, which usually takes about 5 to 10 minutes.

In this condition, the main detergent ingredient, 5

the nonionic substance, along with a minor one.

the amount of acid controlling the pH regulation is added, and the pH value is generally adjusted to such a value, on which the proteolytic enzyme used is on

is best stable. The solution is then stirred, and 10

it is the adjuvants, such as perfume and color, that give the product the properties desired in the final state received, added. Then the protease and amylase enzyme preparations are added to the solutions

., _ and mixed with it; this is the final stage in the 15th

Production of the liquid washing and washing machine according to the invention Detergent product. If desired, the viscosity controlling additive can be added in an earlier Process stage are incorporated.

The work measures described above can be carried out at room temperature be made; In principle, any temperature in the range from 20 to 50 C can be used However, care must be taken that when volatile substances such as perfume are added the temperature is so low that adverse losses are avoided. The received Product generally has a pH in the range from 7 to 10 and a density in the range from 0.9 to 1.1, preferably from 0.95 to 1.05. The viscosity of the end product at 24 C is in the range from 60 to 150 Centipoises, preferably about 80 to 140 centipoises, and particularly expediently about 115 to 135 centipoises, measured with a Brookfield viscometer at room temperature .

Liquid washing and cleaning agent compositions according to the invention are easy to use and have good potency. Compared to powder detergents for white and coarse laundry you can get the same cleaning effect for soiled. Wash with a lower one Achieve volume of liquid detergent according to the invention. For example, if you have an inventive If detergent is used in a typical preferred formulation, one needs for an automatic loaded from above 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) are needed for front-loading machines. Hence the concentration lies of liquid detergent according to the invention in

the wash water on the order of about 0.1%.

Usually the amount of liquid detergent in the washing solution is in the range of about 0.0 to 0.3%, preferably at 0.08 to 0.2% and particularly expediently 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 of a more dilute formulation are used, but required you for larger quantities accordingly additional packaging material, and therefore this is for the Consumers less functional. In addition, with more highly diluted products there is a greater risk that they Freeze in cold climates, and they are more likely to be subject to hydrolysis and other storage and preservation chemical changes.

example 1

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

Ingredient wt.%

Ethoxylated C ₁₂ -C ₁₅ primary alcohol

(7 moles EO / mole alcohol) 32.0

Sodium dodecylbenzenesulfonate 7.0

Triethanolamine 2.8

Ethanol 5.0

Sodium formate 1.0

H ₃ SO ₄ (conc.) 0.7

Optical brighteners ⁽¹⁾ 0.27

(2)

Dye * '0.01

Perfume 0.35

Water rest

(1) A mixture of Phorwite RKH and Phorwite BHC brighteners, made by Verona.

(2) Polar Brillant Blue (PBB) manufactured by Ciba-Geigy.

Enzyme-containing liquid detergent compositions B-U were prepared by adding various amounts of protease undot-amyase enzymes to that previously described Composition A formulated. The enzyme concentration in each of these detergent compositions is in Table I in% by weight of enzyme content, based on the weight of the composition. As a protease enzyme has been used a liquid enzyme preparation used under the trade name "Alcalase" from Novo Industries, Copenhagen, Denmark, and the per gram of enzyme preparation has a concentration of 2.5 Anson units. As fl £ - amylase enzyme has been used a liquid enzyme preparation used under the trade name "Termamyl" from Novo Industries and has a concentration of 120,000 Novo-Amylase units per gram of liquid Possesses enzyme preparation.

Test procedure

A total of 6 cotton rags, 3 of which were stained with ox blood and 3 stained with grass, were placed in each of 4 containers of a U.S. Testing Company manufactured Tergotometer boiler. It was “Carried out a series of washing tests, each with a different liquid detergent of the composition A-U is used in each container of the tergotometer became. The work was carried out under the following test conditions:

Concentration of liquid detergent 0.09% Overturning movement 100 rpm Duration of movement 10 mins What temperature approx. 50 ⁰ C 5 Water hardness approx. 150 ppm as

Calcium carbonate

After washing was complete, the test cloths were rinsed in tap water and then dried. The percentage Stain removal was measured in the manner that before washing and after washing using a Gardner XL-20 Colorimeters a reflectance value was read for each stained test swab. The value percent stain removal (% S.R.) was calculated as follows

(Rd after washing) - (Rd before washing)% SR _{(Rd before leakage} ) _ ( _{Rd before} washing)

therein, "Rd before washing" means the Rd value after staining.

From the values for the percentage of stain removal / which had been obtained for each of the 3 test cloths with the same type of staining became liquid for each of the test cloths examined Detergent composition determined an average value. The results are shown in Table 1. This contains the% S.R. values for each of the tested liquid detergent compositions (compositions A-U) as well as indicated the enzyme concentration in these detergent compositions.

Tabel

Comparison for stain removal with enzyme-containing detergent compositions

.Composition

A.
B.
C.
D.
E.

F.
G
H
I.
.J

K
L.
M.
N
0

Q
R.
S.
T

Wt% protease

0 0J2 0 ^ 4 06

(D

U, O

ο; 8th

00 o; 2

4 6

0.0 02 o! 4

o [8 0.0

⁰ Y ²

4th

06

0J8 0.0

Weight%

0

0

0

0

o; o

0.2 0 0.2 0

⁰ I ²

0.4 0 0 0

0.6 0.6

Of

0.6

0.6 0.8

% Stain remover .Aq

Beef liver blood

42.0 50 8 52.8 53.9 55.5

44.2 55.3 58? 4 60 6 6O, ^J 5

47.1

56 2

58 6 63 3 63.2

47.7 55 4

57 5 60 9

62; o 47.7

grass

37.6 42.4 44 44 44J1

38.3

43 45.0 44? 8 45J0

37.6

fl3 42.1

43.7

44 \ 5

36.5

(1) The proteolytic activity of Alcalase was 2.5 Anson units per gram

Accordingly, a concentration of, for example, 0.2% corresponded to Alcalase in the liquid detergent composition a protease enzyme activity of 0.5 Anson units (0.2 2.5) per 100 g of detergent Composition.

(2) The amylolytic activity of Termamyl was 120,000 Novo-amylase units per gram a concentration of 0.2% Termamyl in the liquid

Detergent with an EC amylase enzyme activity of 24,000 5

Novo-amylase units (0.2 120,000) per 100 g Detergent composition.

Percent Stain Removal (S.R.), which, as in Table 1 given, with which Composition A was achieved, represents that S.R. value which in the absence of Enzymes can be achieved in the detergent composition. If you look at the S.R. values for the cattle blood stains looks at himself and compares this with the S.R. values,

.ε that were achieved with the compositions F, K, P and U, the compositions F, K, P and U all contained amylase enzyme but no protease and were accordingly no detergents according to the invention), it can be seen that the composition P contained the 0.6% by weight of O ^ amylase, the best S.R. Value (47.7%) that can be achieved with amylase enzyme, namely an increase of about 5.7% compared to the S.R. value of 42% for the enzyme-free composition A. Similarly, compares the S.R.values associated with the compositions B, C,

D and E (which are all protease enzymes but not amylase contained) were achieved that the 0.8% protease-containing composition E that achievable with protease enzyme maximum improvement in S.R. value (55.5%) expresses that was an increase of 13.5% based on the value of 42% S.R. achieved with the enzyme-free composition A

334a097

The synergistic effect of the combination of protease and amylase enzymes for the removal of protein-containing Spots can be clearly seen from Table 1. For example, with the composition G, the Contained 0.2% by weight protease and 0.2% by weight amylase enzymes (representing 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 the S.R. value (based on the enzyme-free composition A),

which was found with composition E containing 0.8% by weight of protease. From an economic point of view, that is Use of the composition G, which according to the invention contained a mixture of enzymes, a considerable advance,

because the same effect when using a greatly reduced 15

Amount of relatively expensive protease enzyme, compared with the composition E, is possible.

The highest value for the percentage stain removal 2Q was achieved with the composition N. This 0.6 wt.% Special Composition N containing protease and 0.4% by weight amylase in combination gave a percentage increase of the S.R. value of 21% in the removal of blood stains, based on the enzyme-free composition A. The Value of 63.3% S.R. which could be achieved with the composition N, significantly higher than the maximum S.R. value, the detergent compositions containing only the protease enzyme but not the amylase 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 OC * - amylase enzymes can also recognize when the S. R.-values obtained for the grass stains

. - | _..: · Ο ^'.:: Ho 33Α4097

were considered. For example, with the composition H, the 0.2% amylase and 0.4% protease enzyme contained, achieve a significantly higher S.R. value than with either only the protease enzyme or only the amylase enzyme could be found as detergent compositions each containing single enzyme.

Claims (13)

UEXKÜLt.y StTOLB ^ bis.- ·· european patent attorneys PATENT LAWYERS BESELERSTRASSE 4 D-200O HAMBURG 52 DR JD FRHR. by UEXKULL DR. ULRICH GRAF STOLBERG DIPL-ING. JÜRGEN SUCHANTKE DIPL. ING ARNULF HUBER DR ALLARD by KAMEKE DR KARLHEINZ SCHULMEYEFi COLGATE-PALMOLIVE COMPANY Prio: 13. December 1982 Park Avenue US SN 449 326 New York, New York 100 22 (20 330 ue / thu) V.St.A. December 1983 Liquid detergent and cleaning agent containing enzymes Claims l.j enzyme-containing liquid detergent and cleaning agent composition, marked by: a) about 5 to 75% by weight of one or more detergent surfactants that are 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 O ^ -amylase enzyme, the relative proportionate amounts of these enzymes providing a ratio of the enzyme activities in the mixture of from about 4000 to 80,000 novo-amylase units of O ^ -amylase per Anson unit of protease and the protease is present therein in an amount giving about 0.25 to 2.5 Anson units per 100 g of the detergent composition. 2. Washing and cleaning agent according to claim 1, characterized in that the ratio of the enzyme activities in the enzyme mixture present therein amounts to about 15,000 to 40,000 Novo-amylase units of OL-Asaylase per Anson unit of protease and the protease in one about 0.5 to 2.0 Anson units per 100 grams of detergent compositions is present therein. 3. Washing and cleaning agent composition according to claim 2, characterized in that in the therein present enzyme mixture indicates the ratio of the enzyme activities at about 30 to 40 novo amylase units <α £ amylase per Anson unit is attached to protease. 4. Washing and cleaning agent compositions according to claim 1, characterized in that about 20 to 40% by weight of a nonionic, * water-soluble C ₂ to C ₃ alkoxylated C, _Q to C, g-alkanol detergent and about 4 to 12% by weight of an anionic, water-soluble salt of a C1 to C4, t-alkylbenzenesulfonate detergent is present and in addition about 3 to 15% by weight of a lower alkanol, namely a lower monohydric alcohol with 1 to 4 carbon atoms, a lower polyol having 2 to 3 carbon atoms or a mixture of these substances. 5. Washing and cleaning agent composition according to claim 1, characterized in that it additionally contains about 0/5 to 5% by weight of a water-soluble formate salt and / or a dibasic acid of the formula (CH) (COOH) ₀ wherein η 1 to 6 is available as a viscosity control agent. 6. Enzyme-containing liquid detergent and cleaning agent composition, characterized in that it contains the following components: a) About 20 to 40% by weight of a nonionic detergent compound which consists of an essentially water-soluble C ₂ to C ₃ alkoxylated C to C ₁₈ alkanol; b) about 4 to 12% by weight of an anionic detergent compound, which consists essentially of a water-soluble salt of a C, ~ to C, _g -alkylbenzenesulfonate, c) about 3 to 15% by weight of a lower monoalcohol with 1 to 4 carbon atoms and / or a lower one Polyols having 2 to 3 carbon atoms; d) about 0.5 to 5% by weight of a water-soluble formate salt as a viscosity regulating agent; e) about 35 to 65% by weight of water; and f) an enzyme mixture of essentially alkaline protease enzyme and oil amylase enzyme in a ratio of enzyme activities in the mixture from about 4000 to 80,000 novo amylase units <fl £ amylase per Anson unit of protease yielding relative proportional amounts, with the protease in about 0.25 to 2.5 Anson units per 100 g of detergent compositions Amount is available. 7. detergent and cleaning agent compositions according to claim 6, characterized in that in addition 0.1 to 5% by weight of an alkanolamine are contained. 8. Washing and cleaning agent compositions according to claim 6, characterized in that the enzymes contained in the mixture in such relative proportions that the ratio of the enzyme activities about 15,000 to 40,000 novo amylase units in the enzyme mixture of ^ C-amylase per Anson unit of protease makes up, and the protease in about 0.5 to 2.0 Anson units per 100 grams of the detergent compositions is present. 9. Washing and cleaning agent compositions according to Claim 8, characterized in that the enzymes in the enzyme mixture in such relative proportions Amounts present are such that the ratio of enzyme activities is about 30,000 to 40,000 novo amylase units aniC amylase per Anson unit of protease. 10. Washing and cleaning agent compositions according to claim 6, characterized in that the nonionic detergent compound is a polyethoxylated C, ₂ to C..J- alkanol with 3 to 12 ethylene oxide groups per mole, as the anionic detergent a C, _- or C-alkylbenzenesulfonate, as lower alkanolethanol or a mixture of ethanol and isopropanol, and sodium formate is present as the viscosity control agent. 11. Washing method in which stained and / or soiled Tissue pieces are washed with an enzyme-containing detergent, characterized in that as enzyme-containing detergent uses an enzyme-containing liquid detergent and cleaning agent composition which contains the following components: (a) about 5 to 75% by weight of one or more detergent surfactants, which are anionic, nonionic, cationic, ampholytic and zwitterionic Connections can act; (b) about 25 to 85% water; (c) an enzyme mixture of substantially alkaline protease enzyme and amylase enzyme in a ratio of enzyme activities in the mixture from about 4000 to 80,000 novo amylase units of ^ .- amylase per Anson unit of protease resulting relative proportional amounts, the protease in a about 0.25 to 2.5 Anson units per 100 g of detergent and cleaning agent compositions resulting amount is available. 12. The method according to claim 11, characterized in that 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 ^^ - amylase per Anson unit of protease is, and wherein the protease in about 0.5 to 2.0 Anson units per 100 g of detergent compositions resulting amount is available. BATH ORIGINAL 13. The method according to claim 11 / characterized in that a liquid detergent and cleaning agent composition is used, which essentially consists of the following components: (a) about 20 to 40% by weight of a nonionic surfactant compound of a water-soluble C_ to C, alkoxylated C, - to C, _ft alkanol, (b) about 4 to 12% by weight of an anionic surfactant compound from a water-soluble salt of a C1 to C1 alkylbenzenesulfonate; (c) about 3 to 15% by weight of a lower monoalcohol having 1 to 4 carbon atoms and / or one lower polyols of 2 to 3 carbon atoms; (d) about 0.5 to 5% by weight of a water-soluble formate salt as a viscosity control agent; (e) about 35 to 65 weight percent water; and (f) an enzyme mixture of alkaline protease enzyme and ^ C-amylase enzyme in a ratio the corresponding enzyme activities in the mixture from about 4000 to 80,000 novo amylase units an d £ -amylase per Anson unit of protease relative proportional amounts, the protease being in about 0.25 to 2.5 Anson units each 100 g of the detergent compositions resulting amount is present therein.