DK159501B - LIQUID DETERGENT WITH ENZYM MIXTURE - Google Patents

Description

in

DK 159501 B

The invention generally relates to enzyme-containing liquid detergents suitable for detergents or soaking agents. More particularly, the invention relates to detergents containing mixtures of protease and: amylase enzymes in specific conditions, which provides particularly effective dirt and stain removal during washing.

The formulation of enzyme-containing liquid detergents has been the subject of much attention in the art. The desirability of incorporating enzymes into detergents is primarily due to the efficiency of proteolytic and amylolytic enzymes in the breakdown of protein and starchy materials found on dirty textiles, thereby facilitating the removal of stains, such as dots, bloodstains, chocolate's stains and the like. during washing. However, enzyme materials suitable for detergents, especially proteolytic enzymes, are relatively expensive. In fact, they are usually the most expensive ingredients in a typical commercial liquid detergent, even when present in relatively small quantities. In addition, an excess of enzymes is usually needed in the detergent.

Due to the known instability of enzymes in aqueous agents, an excess of enzymes is usually added to the agent to compensate for the expected loss of enzyme activity during long storage periods. Therefore, the expense associated with the use of enzymes in liquid detergents has so far been a significant deterrent to their widespread commercial use.

Detergents containing enzyme mixtures, e.g. proteases 30 and amylases are broadly described in the art. In the U.S.

Patent No. 3,630,930 is thus described e.g. a granular detergent containing from ca. 0.5 to 20% of enzyme carrier grains, the enzyme grains being comprised of from ca. 0.001 to 10% of mixtures of protease and amylase enzymes in a weight ratio of protease to amylase of 50: 1 to 1: 5.

The specification of British Patent Specification No. 1,240,058 is described 2

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a granular detergent containing a mixture of protease and amylase enzymes in a weight ratio of protease to amylase of 30: 1 to 3: 1, the weight percent of amylase in the agent being from 0.0003 to 3%. In the U.S. U.S. Patent No. 3,931,034 discloses a granular detergent containing a mixture of alkaline protease and α-amylase enzymes in an activity ratio ranging from 100,000 to 400,000 Novo-amylase units of amylase per Anson unit of protease.

While the use of enzyme mixtures in granular detergents is generally described in the patent literature, the mixtures themselves are, accordingly, in most cases so widely described that, e.g. comprises mixtures in which the percentage of protease may vary within 5 orders of magnitude 15 (British Patent Specification No. 1,240,058), or the percentage of amylase may vary within 5 orders of magnitude (U.S. Patent No. 3,630,930), thereby promoting the belief that the greater the amount of enzyme used, the more effective the resultant stain removal will be within such wide ranges. Furthermore, the aforementioned patents are strictly attached to granular agents and therefore provide no teachings with respect to the use of enzyme mixtures in liquid agents.

The present invention provides an enzyme-containing liquid detergent comprising: (a) 5-75% by weight of one or more surfactant detergents selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergent compounds; (b) 25-85% by weight of water; and (c) an enzyme mixture consisting essentially of an alkali c protic enzyme and an α-amylase enzyme, and the enzyme-containing liquid detergent is characterized in that:

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3 the enzyme mixture contains 30,000-50,000 Novo-amylase units of α-amylase per; Anson unit of protease, and the protease being present in an amount such that 0.5-2.0 Anson units per unit are provided. 100 g of detergent.

5

Washing of stained and / or dirty materials is accomplished by contacting such materials with an aqueous solution of the liquid detergent defined above.

10

The present invention is based on the discovery that the amount of alkaline protease enzyme usually required for the removal of proteinaceous stains can be substantially reduced thereby combining an amount of amylase enzyme 15 in accordance with the invention to provide a detergent with equivalent or improved stain removal properties but at substantially reduced manufacturing costs. Contrary to the prior art which recommends mixing proteases and amylases within wide ranges of detergents, the enzyme mixtures described herein are characterized by a synergistic interaction between protease and amylase and include only those mixtures having a narrowly defined activity ratio.

The activities of the alkaline protease and α-amylase enzymes are expressed in Anson units of protease and Novo-amylase units of amylase, respectively. These are commonly used entities in the art to describe the activity under common conditions of enzyme formulations containing protease or amylase enzymes.

According to the invention, the enzyme mixtures contain relative amounts of alkaline protease and α-amylase to provide 30,000-50,000 Novo-amylase units of α-amylase per liter. Anson-35 unit of protease, with an activity ratio from.ca.

30,000 to 40,000 is particularly desirable.

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Of course, the amount of enzyme mixture present in the liquid detergent will depend to some extent on the amount of the agent to be added to the washing solution. For detergents intended for use at concentrations of approx. 0.15% in the washing solution for an automatic household washing machine, a suitable amount of mixture will provide from 0.5 to 2.0 Anson units of protease per 100 g of detergent, and with approx. 1.5 Anson units / 100 g of agent is a particularly preferred protease concentration.

10

The activity of the alkaline protease enzyme is measured as above expressed in Anson units. The Anson hemoglobin method for measuring Anson unit activity is a method known in the art for determining the activity of proteolytic enzymes, and is set forth in "Journal of General Physiology", Vol. 22, pages 79-89 (1939), which is incorporated herein by reference thereto. The modified Anson hemoglobin method can also be used to measure the proteolytic activity, such a modified method is described in the article "Alkali-Resistant Enzyme for Detergents", S.R. Green, Soap and Chemical Specialties, pages 86, 88, 90, 94 and 133, May 1968, the disclosure of which is incorporated herein by reference. In principle, the method uses the alkaline protease enzyme to dissolve a denatured hemoglobin substrate under standard conditions in a buffered aqueous medium at the chosen pH, and the amount of dissolved material is determined by a dye sample with phenol reagent.

The activity of the α-amylase enzyme is measured as previously expressed in Novo amylase units. The standard method for measuring such Novo units is a modification of the SKB method (Sandstedt, Kneen & Blish, Cereal Chemistry 16, 712, (1939)) without the addition of β-amylase. In this method, 20 ml of 35 of a buffered starch solution (prepared by the method described below) is measured in a test tube (diameter 24 mm, length 190 mm) and placed in a water bath with thermostat at a temperature of

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5 37 ° C. After a few minutes of preheating, add 10 ml of the amylase solution to be tested (or v ml of amylase solution + (10-v) ml of water). The contents of the glass are thoroughly mixed and at the same time a stopwatch is started. At appropriate time intervals, 1 ml of the reaction mixture is added to 5 ml of a dilute iodine solution (prepared by the method described below), shaken and transferred to a comparator and the color is compared with the standard color. If the color end point is reached in less than 10 minutes, a more dilute amylase solution or a smaller volume of amylase solution is used.

As a colorimeter, Holy Comparator 607 is used with the glass and amylase standard. (see Redfern Methods for Determination of α-Amylase, Cereal Chemistry 2Λ, 259, (1947)). The α-amylase activity of the sample can be calculated using the following formula:

A = 1430 x V

- where t x a x v 20 A = α-amylase activity in Novo amylase units per grams t = time to color end point reached (minutes) a = weight of sample in grams V = volume to which sample is diluted (ml) 25 v = volume of amylase solution used (ml).

The factor "1430" is not strictly constant, but depends to some extent on the starch quality used. For accurate determinations, the value of the factor was to be calculated using 30 commercially available standard amylase preparations with known activity.

The above-mentioned "dilute iodine solution" is prepared by dissolving 1 ml of iodine; stock solution; and 20 g of potassium iodide in sufficient water to form 500 ml; "iodine stock solution" is prepared by dissolving 11 g of iodine crystals and 22 g of ca 6

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lium iodide in sufficient water to form 500 ml.

The "buffered starch solution" mentioned above is prepared as follows: 10 g of soluble starch (e.g., Merck, Amylum solubile, Soluble Starch, Erg. B.6) calculated as dry matter are slurried with some water . The sludge is added to approx.

200 ml of boiling water. When the starch is completely dissolved, the solution is cooled, transferred to a 1 liter volumetric flask and made up to the mark with water. The starch solution (prepared by dissolving 9.36 g NaCl, 69.00 g KI 2 PO 2, 4.80 g 10 2 H 2 O in sufficient water to form 1 liter).

Finally, the solution is saturated with toluene. The pH of the finished buffered starch solution should be 5.7. The starch solution should be as freshly prepared as possible, but can be stored in the refrigerator for no more than 24 hours. Distilled water is used in all cases.

The enzyme activity of proteolytic and amylolytic enzyme formulations is usually determined, as a practical measure, without carrying out the above-described assay methods. For most of the commercially available liquid enzyme formulations containing protease or amylase enzymes, the enzyme activity is provided by the manufacturer and expressed in Anson units or Novo amylase units (or units directly proportional thereto). Alternatively, the activity of a given enzyme formulation can be determined analytically by a method in which the responsiveness of the enzyme with a protein or starch substrate, as the case may be, is measured under standard conditions and then compared with the responsiveness of reference enzyme formulations of known activity. In one such analytical method, the enzyme responsiveness can conveniently be expressed as the optical density of a sample solution containing the erazime & protein ring and protein or starch, when measured under standard conditions, the higher the optical density, the greater the activity.

35

The appropriate alkaline proteolytic enzymes include the

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7 different commercial liquid enzyme formulations that have been adapted for use in detergents, powder form enzyme formulations also being useful, although as a general rule they are less suitable for incorporation into the liquid detergents available. Thus, suitable liquid enzyme formulations include "AlcalasiP ^ and" Esperase® "sold by Novo Industrier, Copenhagen, Denmark, and" Maxatasa "and" AZ-ProteasiPH sold by Gist-Brocades, Delft, The Netherlands. "Al-calase" is particularly preferred for the present agents.

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Among the suitable liquid α-amylase enzyme formulations are those sold by Novo Industrier and Gist-Brocades under the trademarks "Termarny ^ * 1 and" Maxamy ^, respectively.

An organic solvent is preferably used in combination with water to act as the solvent for the liquid detergent. The preferred organic solvent is a lower alkanol of 1-4 carbon atoms having from 1 to 3 hydroxy groups, preferably 1 or 2. The lower alkanol 20 is most preferably ethanol or a mixture of ethanol and isopropanol, with lower monoalcohols such as propanol and butanol, and lower polyols having 2 to 3 carbon atoms such as ethylene glycol and propylene glycol are useful, although less preferred. The use of primary, secondary and tertiary butanol or n-propanol as the lower alkanol is generally limited to mixtures of the same with ethanol, with ethanol preferably constituting at least 80 to 90% of such mixtures.

It is strongly preferred to use ethanol as the sole alkanol and organic solvent. In mixtures of ethanol 30 and isopropanol, it is preferred that ethanol is the main component, ethanol usually constituting from 60 to 90% of the mixture, preferably approx. 75% (ie in a 3: 1 ratio). Of course, other mixtures of the various alkanols can be used, such as ethanol and propylene glycol, and in such mixtures it is also preferred that ethanol be the main component.

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The agents of the present invention contain one or more surfactants selected from the group of anionic, nonionic, cationic, ampholytic and zwitterionic detergent compounds. The synthetic organic detergents used in the practice of the invention can be any of a large number of such compounds known and thoroughly described in the textbook Surface Active Agents, Volume II of Schwartz, Perry and Berch, published in 1958. by Interscience Publishers, the relevant disclosures of which are hereby incorporated herein by reference.

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The nonionic detergents are usually poly-lower alkoxylated lipophilic agents in which the desired hydrophilic-lipophilic balance is obtained by the addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety. For the present agents, the nonionic detergent used is preferably a poly lower alkoxylated higher alkanol wherein the alkanol has 10 to 18 carbon atoms and wherein the number of moles of lower alkylene oxide (having 2 or 3 carbon atoms) is from 3 to 12. Among such materials, it is preferred to use those wherein 20 the higher alkanol is a higher fatty alcohol having 11 or 12 to 15 carbon atoms and containing from 5 to 8 or 5 to 9 lower alkoxy groups per liter. moth. The lower alkoxy is preferably ethoxy, but in some cases it may be desired mixed with propoxy, the latter, if present, usually constituting a minor (less than 50%) component. Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and contains approx. 7 ethylene oxide groups per moles, e.g. Neodol 25-7 and Neodol 23-6.5, which are manufactured by Shell Chemical Company, Inc. The first 20 is a condensation product of a mixture of higher fatty alcohols with an average of approx. 12 to 15 carbon atoms, with approx. 7 moles of ethylene oxide and the latter is a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups 25 per mole on average is approx. 6.5. The higher alcohols are pri- 9

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many alcohols. Other examples of such detergents include Tergitol® 15-S-7 and Tergitol® 25-S-9, both of which are linear secondary alcohol ethoxylates manufactured by Union Carbide Corporation. The first is a mixed ethoxylation product of a linear secondary alkanol having 11 to 15 carbon atoms with 7 moles of ethylene oxide, and the latter is a similar product, but reacting 9 moles of ethylene oxide.

High molecular weight nonionic agents, such as "Neodol" 45-11, which are similar to ethylene oxide condensation products of higher fatty alcohols, the higher fatty alcohol having 14 to 15 carbon atoms and the number of ethylene oxide groups per liter. mol is c.a. 11, are also useful in the present compositions. Such products are also manufactured by Shell Chemical Company. Other useful nonionic agents are represented by Plurafac® B-26 (BASF Chemical Company), the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides.

the preferred poly-lower alkoxylated higher alkanols achieve the best balance between hydrophilic and lipophilic moieties, 20 when the number of lower alkoxy groups is from approx. 40 to 100% of the number of carbon atoms in the higher alcohol, preferably 40 to 60% thereof. The nonionic detergent is preferably at least 50% of the preferred ethoxylated alkanols. Higher molecular weight alkanols and various other usually solid nonionic detergent compounds and surfactants can aid in the formation of the liquid detergent and, as a result, are usually omitted or limited in amount in the present agents, although minor proportions thereof can be used due to As regards both preferred and less preferred nonionic detergents, the alkyl groups present therein are preferably linear, although a minor degree of light branching can be tolerated, such as by a carbon atom next to or two carbon atoms removed from the terminal 35 carbon atom in the straight chain and far from the ethoxy chain with it

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10 provided that such a branched alkyl group is not longer than 3 carbon atoms. Usually, the amount of carbon atoms in such a branched configuration will be less, rarely exceeding 20%, of the total carbon atom content of the alkyl group. Similarly, although straight-chain alkyl groups terminally bonded to the ethylene oxide chains are highly preferred and are believed to result in the optimal combination of purity, biodegradability and non-gelling properties, a middle or secondary link to the ethylene oxide in the chain occur.

In such a case, it is usually only in a minor amount of such alkyl groups, generally less than 20%, but may, as is the case for the previously mentioned Tergi tolerances, be greater. When propylene oxide is present in the lower alkylene oxide chain, it will usually also be less than 20% thereof and preferably less than 10% thereof.

15

Along with the nonionic detergent, which is the most important synthetic organic detergent in the present liquid detergents, an anionic detergent can be used. The most preferred anionic detergent compounds are the higher (10 20 to 18 or 20 carbon atoms) alkylbenzenesulfonate salts, wherein the alkyl group preferably contains 10 to 15 carbon atoms, the most preferred being a straight chain alkyl group having 12 or 13 carbon atoms. Such an alkylbenzene sulfonate preferably has a high content of 3- (or higher) phenyl isomer and a correspondingly low content (usually well below 50%) of 2- (or lower) phenyl isomers; in other words, the benzene ring is preferably bound to a large extent in the 3-, 4-, 55-, 6- or 7-position of the alkyl group, and the content of isomers in which the benzene ring is attached to the 1- or 2-position is the same. -30 the low. Typical surfactant alkylbenzene sulfonates are described in U.S. Patent No. 3,320,174. Of course, more finely branched alkylbenzenesulfonates may also be used, but are usually not preferred because of their lack of biodegradability.

35

Other anionic detergents that are useful are olefin sulfonic acid.

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1 1 night salts. Generally, these contain long chain alkenyl sulfonates or long chain hydroxyalkanesulfonates (with OH being on the carbon atom not directly linked to the carbon atom bearing the -SO ^ H group). The olefin sulfonate detergent usually comprises a mixture of such types of compounds in varying amounts, often with long chain disulfonates or sulfate sulfonates. Such olefin sulfonates are described in many patents such as U.S. Pat. No. 2,061,618, No. 3,409,637, No. 3,332,880, No. 3,420,875, No. 3,428,654, and 3,506,580, and in British Patent No. 10,129,158. The number of carbon atoms in the olefin sulfonate is usually within the range of 10 to 25, more commonly 10 to 18 or 20, e.g. a mixture of especially 12 ° 14 ° 9 ° C 16 with about 14 carbon atoms, or about 14 carbon atoms, or a mixture of mainly and Clg, with an average of about 16 carbon atoms.

Another class of useful anionic detergents are the higher paraffin sulfonates. These may be primary paraffin sulfonates prepared by reacting long chain α-olefins and hydrogen sulfites, e.g. sodium hydrogen sulfite, or paraffin sulfonates with the sulfonate groups distributed along the paraffin chain, such as the products prepared by reaction of a long-chain paraffin with sulfur dioxide and oxygen under ultraviolet light, followed by neutralization with sodium hydroxide or other suitable base (as in U.S. Patent No. 2,530. 280, No. 2,507,088, No. 3,260,741, and 3,372,188, and in German Patent No. 735,096). The paraffin sulfonates preferably contain from 13 to 17 carbon atoms and will usually be the monosulfonate, but may, if desired, be di-, tri-30 or higher sulfonates. The di- and polysulfonates will typically be used in admixture with a corresponding monosulfonate, e.g. as a mixture of mono- and disulfonates containing up to approx. 30% of the disulfonate. Preferably, the hydrocarbon substituent thereof will be straight-chain, but, if desired, 35 branched paraffin sulfonates may be used, although not so good in biodegradability.

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Other suitable anionic detergents are sufated ethoxylated higher fatty alcohols of the formula R0 (CoH.0) SO 2 M, wherein R is a fatty alkyl group having from 10 to 18 or 20 carbon atoms, m is from 2 to 6 or 8 (preferably having a value of about .

5 is 1/5 to 1/2 of the number of carbon atoms in R) and M is a solubilizing salt-forming cation such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino, or a higher alkylbenzenesulfonate wherein the higher alkyl has 10 to 15 carbon atoms. As is the case with the preferred non-ionic detergent, it is preferred that the alkyl group of the anionic alkoxylated detergent is a mixture of various chain lengths, such as chains of 11, 12, 13, 14 or 15 carbon atoms or chains of 12 and 13 carbon atoms. , rather than all with one chain length.

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Ethylene oxide is the preferred lower alkylene oxide of the anionic alkoxylated detergent, as of the nonionic detergent, and the proportion thereof in the polyethoxylated higher alkanol sulfate is preferably 2 to 5 moles of ethylene oxide groups 20 present. moles of anionic detergent, with three moles being particularly preferred, especially when the higher alkanol has 11 or 12 to 15 carbon atoms. In order to maintain the desired hydrophilic-lipophilic balance when the carbon atom content of the alkyl chain is in the lower portion of the 10-18 carbon atom range, the ethylene oxide content 25 of the detergent can be reduced to approx. two moles per in the higher part of the range, the number of ethylene oxide groups, when the higher alkanol has 16 to 18 carbon atoms, can be increased to 4 or 5 and in some cases to as much as 8 or 9. Similarly, the salt-forming cation can be changed 30 for the best solubility. It may be any suitable solubilizing metal or group, but will most often be an alkali metal, e.g. sodium or ammonium.

If lower alkylamine or alkanolamine groups are used, the alkyl and alkanol groups will usually contain from 35 to 4 carbon atoms and the amines and alkanolamines may be mono-, di- and tri-substituted, as in monoethanolamine, diisopropanolamine and trimethylamine.

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The poly lower alkoxy higher alkanol sulfates may be used in place of or in combination with other preferred anionic detergents such as the higher alkyl benzene sulfonates to supplement the nonionic detergent in the present liquid detergent. A preferred polyethoxylated alcohol sulfate detergent is available from Shell Chemical Company and marketed as "Neodol" 25-3S.

Examples of the higher alcohol polyethene oxy sulphates which can be used in the liquid detergents of the invention include: mixed normal or primary alkyl triethene oxy sulphate, sodium salt; myristyl triethenoxy sulfate, potassium salt; n-decyldiethene oxysulfate, diethanolamine salt; lauryl diethoxy sulfate, ammonium salt; palmityltetraethenoxysulfate, sodium salt; mixed normal primary alkyl mixed tri and tetraethenoxy sulfate, sodium salt; stearyl pentaethenoxy sulfate, trimethylamine salt; and mixed normal primary alkyl triethenoxysulfate, potassium salt.

Other useful anionic detergents include the higher acyl sarcosinates, e.g. sodium N-lauroyl sarcosinate, higher fatty alcohol sulfates such as sodium lauryl sulfate and sodium tallow alcohol sulfate; sulfated oils; sulfates of mono- or diglycerides of higher fatty acids, e.g. stearic monoglyceride monosulfate; although sodium higher alcohol sulfates among these 25 have been found to be inferior to the polyethoxylated sulfates in terms of purity; aromatic poly (lower alkenoxy) ether sulfates, such as the sulfates of the condensation products of ethylene oxide and nonylphenol (usually with 1 to 20 oxyethylene groups per molecule, preferably 2 to 12); 30 polyethoxy higher alcohol sulfates and alkyl phenol polyethoxy sulfates having a lower alkoxy (having 1-4 carbon atoms, e.g. methoxy) substituent on a carbon atom close to that bearing the sulfate group such as monomethyl ether monosulfate of a long chain vicinal glycol, e.g. mixing vicinal alkanediols' 35 with 16 to 20 carbon atoms in a straight chain; acyl esters of glacial acetic acid, e.g. oleylisæthionater; acy1-N-methy1taurider,

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14 e.g. potassium N-methyllauroyl or oleyl taurides; higher alkylphenyl polyethoxysulfonates; higher alkyl phenyl disulfonates, e.g. pentadecylphenyldisulfonat; and higher fatty acid soaps, e.g. mixed coconut oil and tallow soaps in a ratio of 5: 1: 4.

Among the aforementioned types of anionic detergents, the sulfates and sulfonates are usually preferred, but the corresponding organic phosphates and phosphonates may also be used when their phosphorus content is not adverse.

Usually, as previously mentioned, the water-soluble anionic synthetic organic detergents (including soaps) are salts of alkali metal cations such as potassium, lithium and especially sodium, although salts of ammonium and substituted ammonium cations such as those previously described, e.g. triethanolamine, triisopropylamine, may also be used. In the above examples of water-soluble anionic detergent, it must be taken into account that the sodium, potassium, ammonium and alkanolammonium salts are mentioned individually for each detergent.

20

Ampholytic detergents can be used in the present compositions in smaller quantities to replace the anionic detergent or a portion thereof or to replace a portion of the nonionic detergent. Ampholytic detergents include the 25 higher fat carboxylates, phosphates, sulfates or sulfonates containing a cationic substituent such as an amino group which may be quaternized, e.g. with a lower alkyl group, or the chain extension at the amino group by condensation with a lower alkylene oxide, e.g. of ethylene oxide. Usually, the agents containing such ampholytic or cationic detergents will not be as effective and may have a greater tendency to gel or thicken upon standing. Therefore, they are often avoided. If such properties cannot be objected to, minor amounts of ampholytic agents such as "Mirano" C2M, which is sold by Miranol Chemical (S)

Company, or "Deriphar®" 151, a sodium N-coconut / 3-amine propionate sold by General Mills, Inc., however, is used. A cat

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ionic detergent that may sometimes be useful is distearlydimethylammonium chloride (it has a textile softening effect) and the higher fat amine oxides such as bis (2-hydroxyethyl) octadecylamine oxide.

The viscosity control agent used to maintain the desired viscosity in the liquid detergent, prevents gel formation at low temperatures and allows a reduction in the lower alkanol solvent content to be, for example, a water-soluble formate. Sodium formate is preferred, but alkali metal formates may be used, e.g. potassium formate and various other water-soluble formates, including formic acid which may be added to the liquid detergent in which it is dissolved, ionized and / or reacted to form substantially the same type of liquid detergent resulting from the addition of the alkali metal formate in salt form. . Other formulations which may be used are those of water-soluble cations, as previously described, such as salt-forming cations for anionic detergents. Although it is preferred to use the formate viscosity regulating agent, it has been found that various salts of divalent acids can also be used successfully, among which the best appear to be disodium adipate referred to herein as sodium adipate. Other salts of divalent acids of formula (CH CH ^^COOH ^ where n is 1 to 6 may also be used, and in some cases the salts of monounsaturated acids of the same chain length and configuration may be used. However, it is strongly preferred that It is more preferred to use those in which n is 3 to 5, most preferably 4, and in which the acid is completely neutralized, but the acid salts may also be used.

Among the divalent acids which can be used, either as mono- or disaltic ones, are malonic, amber, glutaric, adipic and pimelin acids. An unsaturated divalent acid, maleic acid, can also be used, at least in part. The acids can be used without prior treatment.

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16, or can be used as their salts, such as disodium malonate, monocalcium succinate, triethanol amine glutarate, disodium adipate and monosodium pimelate.

In order to assist in the solubilization of the detergents and optical cleaners which may be present in the liquid detergents, a small amount of alkaline material or a mixture of such materials is often included in the present formulations. Suitable alkaline materials include 10 mono-, di- and trialkanolamines, alkylamines and ammonium hydroxides. Among these, the preferred materials are the alkanol amines, preferably the trialkanolamines, and among them especially triethanolamine. The pH of the finished liquid detergent containing such a basic material will usually be neutral or slightly basic. Satisfactory pH ranges are from 7 to 10, preferably from ca. 7.5 to 9, and more preferably from ca. 7.5 to 8.5.

The optical fluorescent detergents or whiteness promoters used in the liquid detergents are important constituents of modern detergents that give washed laundry and materials a clear appearance so that the laundry is not only clean but also clean. While it is possible to use a single detergent for a particular purpose in the present liquid detergent, it is generally desirable to use mixtures of detergents which will have good clarifying effects on cotton, nylon, polyesters and mixtures of such materials. and which are also pale stable. A good description of such types of 30 optical cleaners is provided in the article "The Requirements of Present Day Detergent Fluorescent Whitening Agents" by Δ.Ε. Siegrist, J. Am. Oil Chemists Soc., January 1978 (Vol. 55). This article and U.S. U.S. Patent No. 3,812,041, issued May 21, 1974, both of which are incorporated herein by reference to their respective disclosures, contains detailed descriptions of a large number of suitable optical clarifiers.

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Among the detergents useful in the present liquid detergents are: "Calcofluor" 5BM (American Cyanamid); "Calcofluor White" ALF (American Cyanamid); "SOF" A-2001 (Ci-ba); Davis); "Phorwite" RKH, "Phorwite" BBH 5 and "Phorwite" BHC (Verona); "CSL", powder, acid (American

Cyanamid); "FB" 766 (Verona); "Blancophor" PD (GAF); "ONPA" (Geigy); "Tinopal® RBS 200 (Geigy). The acidic or" nonionic "forms of the clarifiers tend to be solubilized by alcohols in the present formulations, while the salts tend to be water soluble.

Adjuvants may be present in the liquid detergent to give it additional properties, either functional or aesthetic. Included among the useful excipients are dirt suspending agents or antigen-depositing agents such as polyvinyl alcohol, sodium carboxymethyl cellulose and hydroxypropyl methyl cellulose; thickeners, e.g. gums, alginates, agar agar; foam enhancers, e.g. laurine myristine diethanolamide; antifoaming agents, e.g. silicones; bactericides, e.g. tribromosalicylanilide, hexachlorophen; dyes; pigments (water dispersible); preservatives; ultraviolet absorbents; fabric-softening agents; means for promoting opacity, e.g. polystyrene suspensions and perfumes. Such materials will, of course, be selected according to the desired properties of the finished product and be compatible with the other components thereof. Other excipients which may be employed are divalent or trivalent lower alcohols which, in addition to being solvents and reducing the flash point of the product, may act as antifreeze components and may improve the compatibility of the solvent system with particular product components. Among these compounds, the most preferred group includes the lower polyols having 2 to 3 carbon atoms, e.g. ethylene glycol, propylene glycol and glycerol, but the lower alkyl (C C-C ^) etheric derivatives of such compounds

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18 looks known as Cellosolve can also be used. The proportions of such substitutes for the lower alkanols will be limited, usually being kept at no more than 20% of the total alcoholic strength of the liquid detergent.

5

Another category of useful additives are hydrotropic agents which serve to improve the solubility in aqueous solution of components that otherwise have limited solubility in water. Useful hydrotropic agents include the alkali metal, ammonium-10 and ethanolamine salts of the following acids: (1) arylsulfonic acids such as benzenesulfonic acid and C 1 -C 4 alkyl-substituted benzenesulfonic acids, e.g. toluene sulfonic acid and xylene sulfonic acid; and (2) Cj-Cg alkyl sulfuric acids such as hexyl sulfuric acid.

The amounts of the various components of the present liquid detergents are important for the preparation of a uniform product of the desired viscosity and acceptable vigorous washing effect which does not gel at low temperatures or when left in an open container at room temperature.

20

To improve the solubility of the fluorescent detergents and other ingredients in the detergent and to produce a clear, homogeneous and light flowing liquid product, from 10 to 60% of the total liquid detergent concentrate should be nonionic detergent. Preferably, especially when an anionic detergent is present in the liquid product, the proportion of the nonionic detergent is from 20 to 40% and more preferably 30 to 40%, with the best formulations known at present including . 32%.

The proportion of anionic detergent will usually range from 3 to 15%, preferably 4 to 12%, and most preferably 6 to 10%, with the best formulation known at present including approx. 7% thereof. The ratio of total nonionic detergent to anionic detergent will usually be from 15: 1 to 1: 1, with 8: 1 to 2: 1 being preferred, and 5: 1 to 3: 1 being particularly preferred.

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The lower alkanol in the liquid detergent will generally be present in a sufficient amount to help dissolve and / or stabilize the various components of the finished product, the lower alkanol yields used will generally be from about 1 3 to 15%, 5 preferably 4 to 12%, more preferably 4 to 8% and at present most preferably about 5%.

The viscosity regulating agent used, or a mixture of such agents, will usually comprise from ca.

* 0.5% to 5% of the finished liquid detergent, preferably approx. 0.5 to 3% and most preferably approx. 1%.

The percentage of water, the major solvent in the present compositions, will be from 15 to 85% by weight, preferably 35 to 65% by weight, and most preferably from 40 to 55% by weight of the liquid. In the most preferred formulations, there will be approx. 45 to 50% water.

The content of the alkaline additive, such as triethanolamine, in the liquid agent is usually from ca. 0.1 to 5% by weight of the agent and preferably 1 to 3% by weight thereof. The total proportion of optical brightening agent is usually from approx. 0.05 to 1.5%, preferably approx. 0.1 to 1% and most preferably about 0.2 to 0.5%.

The liquid detergents of the present invention can be prepared by simple manufacturing techniques. In a typical preparation method, the optical clarifiers are slurried in the monovalent alcohol, whereupon water is added to the slurry along with a small amount of a base such as triethanolamine which helps partially dissolve the previously suspended material. Addition of the anionic detergent compound usually results in solution 55 of the remainder of the clarifier to form a clear solvent.

DK 159501 B

20. The viscosity control agent is then added as the acid, acidic salt or completely neutralized salt, preferably the sodium or potassium salt, and stirring is continued until the solution becomes clear, which can usually take approx. 5 to 10 minutes. At this point, the principal detergent, the nonionic, is added together with a minor amount of acid, for the purpose of regulating the pH, the pH generally being set to a value at which the proteolytic enzyme used is most stable.

This is followed by stirring of the solution and the addition of auxiliaries, such as perfume and dye, to give the product its final desired properties. The protease and α-amylase enzyme preparations are then added to the solution and thus mixed as the final step in preparing the liquid detergent product. If desired, the viscosity regulating additive may be incorporated earlier in the procedure.

The above operations can be carried out at room temperature, although suitable temperatures within the range of 20 to 20 ° C may be used, as desired, with the proviso that when volatile materials such as perfume are added, the temperature should be sufficiently low to avoid unfortunate losses. The product obtained will usually have a pH within the range of from 7 to 10, and a density within the range of from 0.9 to 1.1, preferably from 0.95 to 1.05. The viscosity of the finished product at 24 ° C will be in the range of 60 to 150 centipoise, preferably from ca. 80 to 140 centipoise, and most preferably from ca. 115 to 135 centipoise, according to measurements carried out with a Brookfield vis-cosimeter at room temperature.

The present liquid agents are effective and easy to use. Compared to powerful laundry detergent powders, much smaller volumes of the present 35 liquids are used to achieve comparable cleaning of dirty laundry. For example, to use a typical preferred formulation

DK 159501 B

21 of the present invention, only about 60 g or a quarter cup of liquid required for a complete wash of laundry in an automatic top-loading washer in which the volume of water is 55 to 75 liters (15 to 18 gallons); 5 and even less (about 1/2) is needed for front-loading machines. Thus, the concentration of the liquid detergent in the wash water is of the order of approx.

0.1%. Usually, the amounts of the volatile agent in the wash solution will be in the range of from about. 0.05 to 0.3%, preferably from 0.08 to 0.2% and more preferably from ca. 0.1 to 0.15%. The amounts of the various constituents of the liquid agent may vary accordingly. Similar results can be obtained by using larger amounts of a more diluted formulation, but the larger amount needed will require additional packaging and will generally be less suitable for consumer use. In addition, more heavily diluted products will be more likely to freeze in cold weather and may be more susceptible to hydrolysis and chemical changes upon storage.

20

Example 1.

A liquid detergent (not containing enzymes) referred to as agent "A" was prepared at room temperature by mixing the following components in said conditions:

Component Weight%

Ethoxylated C 2 -C 15 32.0 primary alcohol (7 moles 30 EO / mole of alcohol)

Sodium dodecylbenzenesulfonate 7.0

Triethanolamine 2.8

Ethanol 5.0

Sodium formate 1.0 L 2 SO 2 (concentrated) 0.7

Optical Clarifiers} 0.27 35v - ·> (2)

Dye '; 0.01

Perfume 0.35

Water up to 100%

DK 159501 B

22 (1) A mixture of "Phorwite" RKH and "Phorwite" BHC clearing agents negotiated by Verona.

(2) "Polar Brilliant Blue" (PBB) negotiated by Ciba-Geigy. 5

Enzyme-containing liquid detergents B-U were formulated by adding different amounts of protease and α-amylase enzymes to the agent described above.

The protease enzyme used was a liquid enzyme formulation sold under the name "Alcalase" by Novo Industrier, Copenhagen, Denmark, with a concentration of 2.5 Anson units per grams of enzyme preparation. The α-amylase enzyme used was a liquid enzyme formulation sold under the name "Thermamyl" by Novo Industrier, with a concentration of 120,000 Novo amylase units per liter. grams of liquid enzyme preparation.

Test method.

A total of 6 cotton samples, 3 stained with oxblood blood and 3 stained with grass, were placed in each of 4 bowls in a Tergoto meter container manufactured by U.S. Pat. Testing Company. A series of washing experiments were performed using a different liquid detergent from means A-U in each Tergotometer dish under the following test conditions:

Liquid detergent concentration 0.09%

Stirring 100 rpm 30 Stirring time 10 min.

Water temperature 49 ° C

Water hardness approximately 150 ppm as calcium carbonate 35

At the end of the wash, the fabric samples were rinsed in tap water and then dried. The percentage stain removal

DK 159501 B

23 was measured by reading the reflection coefficient for each spotted fabric sample before and after washing, using a Gardner XL-20 colorimeter, and the percent stain removal (% SR) was calculated as follows: 5 n r t, ( Rd after washing) - (Rd before washing) * 6 b.xi. - "" "(Rd before staining) - (Rd before washing) wherein" Rd before washing "denotes the Rd value after staining.

The average of the percent stain removal values calculated for each. the three fabric samples with a plain stain were calculated for each liquid detergent tested. The results are shown in Table I, showing the percentage S.R. for each of the liquid detergents tested (agents A-U) and the enzyme concentration in such detergents.

20 25 30 35

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24

Table I.

Comparative stain removal with enzyme-containing detergents 5% by weight,% by weight, ~ \

Agent protease *; ct-amyl azel% Stain Removal

Bovine liver blood Grass A 0.0 0.0 42.0 31.5 B 0.2 0.0 50.8 37.6 10 C 0.4 0.0 52.8 36.7 D 0.6 0, 0 53.9 36.8 E 0.8 0.0 55.5 36.1 F 0.0 0.2 44.2 37.6 G 0.2 0.2 55.3 42.4 H 0.4 0.2 58.4 44.8 I 0.6 0.2 60.6 44.5 J 0.8 0.2 60.5 44.1 K 0.0 0.4 47.1 38.3 L 0.2 0.4 56.2 43.4 M 0.4 0.4 58.6 45.0 N 0.6 0.4 63.3 44.8 O 0.8 0.4 63.2 45, 0 20 - P 0.0 0.6 47.7 37.6 Q 0.2 0.6 55.4 41.3 R 0.4 0.6 57.5 42.1 S 0.6 0.6 60 , 9 43.7 T 0.8 0.6 62.0 44.5 25 U 0.0 0.8 47.7 36.5 (1) The proteolytic activity of Alcalase is 2.5 Anson units per gram. A concentration of e.g. Thus, 0.2% Alcalase 30 in the liquid detergent corresponds to a protease enzyme activity of 0.5 Anson units (0.2 x 2.5) per ml. 100 g of detergent.

(2) The amylolytic activity of Termamyl is 120,000 Novo 35 amylase units per gram. Therefore, a concentration of 0.2% Thermamyl in the liquid detergent corresponds to an α-amylase enzyme activity of 24,000 Novo amylase units (0.2 x 120,000) per liter. 100 g of detergent.

DK 159501 B

25

As indicated in Table I, the percentage stain removal (SR) obtained by Agent A denotes SR obtained in the absence of enzymes in the detergent. Referring to SR data for axillary blood stains, a comparison of SR which is obtained with agents F, K, P and U, all of which contain amylase enzyme but no protease and therefore not in accordance with the invention, that agent P containing 0.6 wt. of α-amylase provided the greatest improvement in SR (47.7%) obtainable with amylase enzyme, i.e. an increase of approx. 5.7% relative to the SR value of 42.0% for the enzyme-free agent A. Similarly, a comparison of SR obtained with agents B, C, D and E, all of which contain protease enzyme, shows no amylase that Agent E containing 0.8% protease provided the greatest improvement in SR (55.5%) with protease enzyme, i.e. an increase of approx. 13.5% 10 compared to the 42% S.R. obtained with enzyme-free agent A.

The synergistic mutual influence of protease and amylase enzymes for the removal of proteinaceous stains is clearly shown in Table I. Thus, e.g. agent 20 G containing 0.2 wt% protease and 0.2 wt% amylase enzymes (corresponding to an amylase / protease enzyme activity ratio of 24,000 Novo amylase units per 0.5 Anson units) almost the same improvement in S.R. (relative to enzyme-free agent A) as obtained with 0.8 wt% protease in agent E.

From an economic point of view, the use of agent G containing a mixture of enzymes in accordance with the invention clearly represents a substantial reduction in the need for the relatively expensive protease enzyme, compared to agent E.

30

In particular, the combination of 0.6 wt% protease and 0.4 wt% amylase in Agent N provided an increase greater than 21% in percent S.R. for the platelet relative to the 55 enzyme-free agent A. The 63.3% S.R. obtained by agent

Claims (1)

Thus, DK 159501B N is significantly higher than the largest S.R. that could be obtained with detergent-containing detergent detergents without the presence of α-amylase. The amylase / protease enzyme activity ratio of such agent N is 48,000 Novo amylase units per 1.5 Anson units. The synergistic mutual influence of protease and ct-amyase enzymes is equally evident in the S.R. data for the grass stain. Thus, e.g. agent H containing 0.2% amylase and 0.4% protease enzymes a significantly higher S.R. than could be obtained with detergents containing either protease or amylase as single enzymes in the agent. Patent claims. Enzyme-containing liquid detergent comprising: (a) 5-75% by weight of one or more surfactant detergents selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergent compounds (b) 25-85% by weight of water, and (c) an enzyme mixture consisting essentially of an alkaline protease enzyme and an α-amylase enzyme, characterized in that the enzyme mixture contains 30,000 to 50,000 Novo-Amylase units as defined in the description of oC-amylase per liter. Anson unit of protease, the protease being present in an amount such that 0.5-2.0 Anson units per unit are provided. 100 g of detergent.