FI74731C - Liquid detergent composition containing an enzyme mixture. - Google Patents

Description

1 74731

This invention relates generally to liquid detergent compositions containing enzymes suitable for detergent and soaking agent recipes. In particular, the invention relates to detergent compositions comprising mixtures of protease and amylase enzymes in certain proportions which provide a particularly effective removal of dirt and stains during washing.

The formulation of liquid detergent compositions containing enzymes has been of great interest in the prior art. It is desired to add enzymes to detergent compositions, firstly because proteolytic and amylolytic enzymes efficiently degrade proteinaceous and starchy substances present in dirty textiles and thus facilitate the removal of stains such as grease, blood, chocolate and the like during washing. However, enzyme agents suitable for detergent compositions are relatively expensive, especially proteolytic enzymes. In fact, they are the most expensive ingredients in a typical commercial liquid detergent composition, although they are present in relatively small amounts. But usually an excess of enzymes must be present in the detergent recipe. Due to the known instability of the enzymes in aqueous mixtures, excess enzymes are usually added to the recipe to compensate for the decrease in enzyme efficiency during longer storage, as expected. Therefore, the costs associated with the use of enzymes in liquid detergent compositions have hitherto been a significant barrier to their wider commercial use.

Detergent compositions comprising mixtures of enzymes, for example proteases and amylases, have been extensively described in the prior art. For example, U.S. Patent 3,630,930 discloses a detergent composition in the form of granules containing about 0.5-20% granules of an enzyme carrier and the enzyme granules containing about 0.001-10% of 2,74731 mixtures of protease and amylase enzymes in a weight ratio of protease: amylase 50: 1 to 1: 5. British Patent 1,240,058 discloses a detergent composition in the form of granules containing a mixture of protease and amyla enzymes in a weight ratio of protease: amy1a si of 30: 1 to 3: 1, and the proportion by weight of Amylase in the mixture is 0.0003 to 3%. . U.S. Patent 3,931,034 discloses a detergent composition in the form of granules containing an alkaline mixture of protease and α-amylase enzymes in a ratio of from 100,000 to 400,000 Novo amylase units of amylase per Anson unit of protease.

The use of enzyme mixtures, usually in the form of granular detergent compositions, is described in the patent literature, but in most cases the compositions themselves are described so broadly as to contain, for example, mixtures in which the percentage of protease can vary by 5 (British Patent 1,240,058) or amylase. can vary in magnitude by 5 (U.S. Patent 3,630,930), which encourages the belief that within such wide limits it would be possible to result in more effective stain removal the greater the amount of enzyme used. In addition, the aforementioned patents, as well as U.S. Patent 3,931,034, are strictly limited to those in the form of granules; mixtures and do not provide information on the use of enzyme mixtures in liquid mixtures.

The present invention provides an enzyme-containing liquid detergent composition comprising: (a) from about 5 to about 75 weight percent of one or more surfactant detergents selected from the group consisting of anionic, nonionic, cationic, ampholytic, and amphoteric ion-containing compounds; (b) about 0.5-5% by weight of a viscosity regulator selected from the group consisting of water-soluble formate salts and dibasic acids of the formula (CH 2) n (CO 2 H) 2, wherein n is 1-6, (c) about 25-85% water; and 3,74731 (d) an enzyme mixture comprising predominantly an alkaline protease enzyme and an α-amylase enzyme in a ratio such that the ratio of the effects of the enzymes in said mixture is from about 4,000 to about 80,000 Novo-amyl units per α-amylase per Anson unit of protease, and said protease is present in such an amount that there are from about 0.25 to about 2.5 Anson units per 100 g of detergent composition.

According to the method of the invention, the washing of stained and / or dirty materials is carried out by contacting these materials with an aqueous solution of a liquid detergent mixture as defined above.

The present invention is based on the finding that the amount of alkali protease enzyme normally required to remove a proteinaceous stain can be greatly reduced by incorporating an amount of amylase enzyme in accordance with the invention to provide a detergent composition having equivalent or improved stain removal capabilities. lower prescription costs. In contrast to prior art reports that recommend mixing proteases and amylases within very wide limits with detergent compositions, the enzyme compositions described herein are known for the synergistic interaction of protease and amylase, and include only those compositions having a well-defined relationship of effects.

The effects of temporal protease and α-amylase enzymes are expressed in Anson units for protease and in Novo amylase units for amylase, respectively. These are units commonly used in the art and describe - under ordinary circumstances - the effect of enzyme recipes containing protease or amylase enzymes.

In a preferred embodiment of the invention, the enzyme mixtures contain relative amounts of alkaline protease and α-Amylase, corresponding to about 10,000 to 50,000 Novo amylase units of α-amylase per Anson unit of protease, and an effect ratio of about 15,000 to 40,000 is preferred. a ratio of about 30,000 to 40,000 is considered particularly good.

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The amount of enzyme mixture present in the liquid detergent mixture will, of course, depend to some extent on the amount of mixture added to the washing solution. In detergent compositions intended to be used at a concentration of about 0.15% in an automatic home washing machine wash solution, a suitable amount of composition corresponds to about 0.25 to about 2.5 Anson units of protease per 100 g of detergent composition, and a ratio of about 0.5 to 2.0 is preferred, and a protease concentration of about 1.5 Anson units / 100 g of mixture is considered particularly good.

The effect of the alkaline protease enzyme is measured, as mentioned above, in Anson units. The Anson Hemoglobin Method for Measuring the Effect of the Anson Unit is a well-known method in the art for determining the effect of proteolytic enzymes and is described in Journal of General Physiology, Part 22, pages 79-89 (1939), and this description is incorporated herein by reference. A modified Anson hemoglobin method can also be used to measure proteolytic activity, and such a modified method is described in "Alkali-Resistant Enzyme for Detergents", S.R. Green, Soap and Chemical Specialties, pages 86, 88, 90, 94 and 133, May 1968, which is incorporated herein by reference. The method utilizes in principle an alkaline protease enzyme to degrade denatured hemoglobin substrate under standard conditions in a buffered aqueous medium at a selected pH and the amount of degraded material can be determined by a colored phenol reagent.

The effect of the α-amylase enzyme, as mentioned above, is measured in Novo amylase units. The standard measurement method for Novo units is a variant of the SKB method (Sandstedt,

Kneen 8. Blish, Cereal Chemistry 16, 712, (1939) without the addition of β-amylase. In this method, 20 ml of buffered starch solution (prepared by the method described below) is weighed into a test tube (diameter 24 mm, length 190 mm) and placed in a water thermostat at 5 74731 37 ° C. After preheating for a few minutes, 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 tube are mixed well and at the same time the stopwatch is started. At appropriate intervals, add 1 ml of the reaction mixture to 5 ml of dilute iodine solution (prepared by the method described below), shake and transfer to a reference tube and compare the color with the standard color. If the color end point is reached in less than 10 minutes, use more diluted amylase solution or a smaller volume of amylase solution.

A calorimeter with a Hellige Comparator 607 glass α-amylase standard is used (cf. Redfern Methods for the determination of α-amylase, Cereal Chemistry, 2 £ 259, (1947)). The α-amylase activity of the sample can be calculated using the following formula:

A = 1430 x V

- where txaxv A = effect of α-amylase in Novo amylase units per gt = time taken to reach the end point of the color (min) a = weight of the sample in grams V = volume to which the sample is diluted (ml) v = volume of amylase solution used (ml) .

The factor "1430" is not an absolutely exact constant, but depends to some extent on the quality of the starch used. For accurate measurements, the factor value should be calculated using a commercially available standard amylase preparation with a known effect.

The above-mentioned "dilute iodine solution" is prepared by dissolving 1 ml of "stock iodine solution" and 20 g of potassium iodide in a sufficient amount of water to give 500 ml; a "stock iodine solution" is prepared by dissolving 11 g of iodine crystals and 22 g of potassium iodide in a sufficient amount of water to give 500 ml. The above-mentioned "buffered starch solution" 6 74731 is prepared as follows: 10 g of soluble starch (e.g. Merck, Amylum solubile, Soluble Starch, Erg. B.6) calculated as dry matter are prepared as a slurry with a small amount of water. The slurry is added to about 200 ml of boiling water. When the starch is completely dissolved, cool the solution, transfer to a 1 liter volumetric flask and make up to the mark with water. Starch solution (made by dissolving 9.36 g NaCl, 69.00 g KI 2 PO 4, 4.80 g 2 L 2 O in a sufficient amount of water to give 1 liter of solution). Finally, the solution is saturated with toluene. The pH of the finished buffered starch solution should be 5.7. The starch solution must be as freshly prepared as possible, but can be stored in the refrigerator for a maximum of 24 hours. In all cases, distilled water is used.

The enzymatic activity of proteolytic and amylolytic enzyme preparations is usually determined as a practical measure without performing the test method described above. For most commercially available liquid enzyme preparations containing protease and amylase enzymes, the potency values of the enzyme are provided by the manufacturer and are expressed in Anson units or Novo amylase units (or units directly comparable to them). Alternatively, the effect of a particular enzyme preparation can be readily determined analytically by a method in which the reactivity of the enzyme with the protein or starch substrate in question is measured under standard conditions and then compared to reference enzyme preparations of known activity. In such an analytical method, the reactivity of the enzyme can be conveniently expressed as the optical density of the test solution containing the enzyme preparation and the protein or starch substrate, measured under standard conditions, and the stronger the effect, the higher the optical density.

Suitable temporal proteolytic enzymes include various commercial liquid enzyme preparations adapted for use in detergent compositions, but enzyme preparations in powder form are also useful, although, as a rule, they are less easy to add to the detergent compositions in question. Suitable liquid enzyme preparations are thus, for example, "Alcalase" and "Esperase" sold by Novo Industries, Copenhagen, Denmark, and "Maxatase" and "Az-Protease" sold by Gist-Brocades, Delft, The Netherlands. "Alcalase" is considered particularly good for the mixtures in question.

Suitable liquid α-amylase enzyme preparations are those sold by Novo Industries and Gist-Brocades under the trademarks "Termamyl" and "Maxamyl", respectively.

The organic solvent is preferably used together with water as a solvent for the liquid detergent mixture. The preferred organic solvent is a lower alkanol having 1 to 4 carbon atoms and 1 to 3 hydroxy groups, primarily 1 or 2. The lower alkanol is most preferably ethanol or a mixture of ethanol and isopropanol, and lower monoalcohols such as propanol and butanol and lower polyols having 2-3 carbon atoms such as ethylene glycol and propylene glycol are suitable but less popular. The use of primary, secondary and tertiary butanol or n-propanol as a lower alkanol is usually limited to mixtures thereof with ethanol, and ethanol is preferably present in at least 80-90% of such mixtures. It is highly preferred to use ethanol as the sole alkanol and organic solvent. In mixtures of ethanol and isopropanol, it is preferred that ethanol be the major component, usually 60-90% of the mixture, preferably about 75% (i.e. in a ratio of 3: 1). Of course, other mixtures of different alkanols can also be used, such as ethanol and propylene glycol, and even in these mixtures it is preferred that ethanol be the main component.

The compositions of the present invention contain one or more surfactants selected from the group consisting of anionic, nonionic, cationic, ampholytic and 8,74731 amphoteric detergent compounds. The synthetic organic detergents used in the practice of the invention may be any of a wide variety of such compounds which are well known and are described in detail in Surface Active Agents, Part II, Schwartz,

Perry and Berch, a publisher in 1958, Interscience Publishers, and related commentaries are attached as a literature source.

Nonionic detergents are usually lipophilic poly-lower alkoxy compounds in which the desired hydrophilic-lipophilic balance is obtained by adding a hydrophilic poly-lower alkoxy group to the lipophilic moiety. The nonionic detergent used in the mixtures in question is a higher alkanol containing mainly poly-lower alkoxy groups, in which the alkanol contains 10 to 18 carbon atoms and in which the number of lower alkylene oxy moles (2 or 3 carbon atoms) is 3 to 12. Of these substances, it is preferred to use those in which the higher alkanol is a higher fatty alcohol having 11 or 12 to 15 carbon atoms and containing 5 to 8 or 5 to 9 lower alkoxy groups per mole. The lower alkoxy is preferably ethoxy, but in some cases it may be used in combination with propoxy and the latter, if present, is usually a minor component (less than 50%). Examples of these compounds are those in which the alkanol contains 12 to 15 carbon atoms and contains about 7 ethylene oxide groups per mole, for example, Neodol 25-7 and Neodol 23-6.5, sold by Shell Chemical Company, Inc. The former is a higher-fat a condensation product of a mixture of alcohols having an average of 12 to 15 carbon atoms and about 7 moles of ethylene oxide, and the latter corresponds to a mixture having 12 to 13 carbon atoms in the higher fatty alcohol and an average number of ethylene oxide groups per mole of about 6.5. Higher alcohols are primary alkanols. Other examples of such detergents are Tergitol 15-S-7 and Tergitol 15-S-9, both of which are straight chain secondary alcohol ethoxylates manufactured by Union Carbide Corporation. The former is a mixed ethoxylation product of a straight-chain secondary alkanol containing 11 to 15 carbon atoms, 9,74731 atoms, with 7 moles of ethylene oxide, and the latter is a similar product, but nine moles of ethylene oxide have been present in the reaction.

Also useful in these compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, and the higher fatty alcohol contains 14-15 carbon atoms and the number of ethylene oxide groups per mole is about 11. Such products are also manufactured by Shell Chemical Company. Other useful nonionics include Plurafac B-26 (BASF Chemical Company), a reaction product of a higher straight chain alcohol and ethylene and propylene oxides.

Preferred poly-lower alkoxy-higher alkanols provide the best balance of hydrophilic and lipophilic moieties when the number of lower alkoxy groups is about 40% to 100% of the number of carbon atoms in the higher alcohol, preferably 40-60% thereof. The nonionic detergent preferably contains at least 50% of the preferred ethoxy alkanols. Higher molecular weight alkanols and several other normally solid nonionic detergent compounds and surfactants can contribute to the gelation of the liquid detergent composition and are thus usually avoided or limited in the compositions in question, although smaller amounts may be used due to their detergent properties. reasons. With respect to both preferred and less preferred nonionic detergents, the alkyl groups therein are preferably straight chain, although a slight slight branching may be acceptable, such as on a carbon atom following the straight chain end or two carbon atoms and not in the ethoxy chain. that this branched alkyl is not more than three carbon atoms in length. The proportion of carbon atoms in such a branched configuration is usually smaller.

10 74731 rarely more than 20% of the total carbon atom content of the alkyl.

Likewise, although straight-chain alkyls, which are bound to ethylene oxide chains at their ends and are considered to result in the optimal combination of washability, natural decomposition and non-gelling, are definitely preferred, ethylene oxide incorporation in the chain may also occur centrally or secondarily. In that case, only a smaller proportion of such alkyls is present, usually less than 20%, but the proportion may be higher for the aforementioned Tergitols. Similarly, if propylene oxide is present in the lower alkylene oxide chain, it is usually less than 20% and preferably less than 10%.

In addition to the nonionic detergent, which is the main synthetic organic detergent in the liquid detergent compositions in question, an anionic detergent may be used. Preferred anionic detergent compounds are higher (10-18 or 20 carbon atoms) alkyl benzene sulfonate salts in which the alkyl group preferably contains 10-15 carbon atoms, and is most preferably a straight chain alkyl radical of 12 or 13 carbon atoms. Such an alkylbenzene sulfonate has a high content of 3- (or higher) phenyl isomer and a correspondingly low (usually much less than 50%) content of 2- (or lower) phenyl isomer; in other words, the benzene ring is largely attached to the 3-, 4-, 5-, 6- or 7-position of the alkyl group and the isomer content at which the benzene ring is attached to the 1- or 2-position is low, respectively. Typical alkyl benzene sulfonates as surfactants are described in U.S. Patent 3,320,174. Of course, very richly branched alkyl benzene sulfonates can also be used, but are not generally considered good because they do not degrade in nature.

Other anionic detergents that are useful include olefin sulfonate salts. These usually contain long-chain alkenyl sulfonates or long-chain hydroxyalkane sulfonates (in which OH has a carbon atom 74731 sa which is not directly attached to a carbon atom containing an -SO2H group). The olefin sulfonate detergent usually contains a mixture of these types of compounds in varying amounts, often in combination with long chain disulfonates or sulfate sulfonates. These olefin sulfonates are described in several patents, such as U.S. Patent Nos. 2,061,618, 3,409,637, 3,332,880, 3,420,875, 3,428,654, 3,506,580, and British Patent No. 1,129,158. Number of Carbon Atoms the olefin sulfonate usually has between 10 and 25, more usually between 10 and 18 or 20, for example a mixture of predominantly C 1-4 / C 3a C 6 g with an average of about 14 carbon atoms, or a mixture mainly of C C18 has an average of about 16 carbon atoms.

Another useful class of anionic detergents are higher paraffin sulfonates. These may be primary paraffin sulphonates prepared by reacting long-chain alpha-olefins with bisulphites, for example sodium bisulphite, or paraffin sulphonates with sulphonate groups along the paraffin chain in the paraffin chain, as in products prepared by long-term paraffin followed by neutralization with sodium hydroxide or other suitable base (as in U.S. Patents 2,503,280, 2,507,088, 3,260,741, 3,372,188, and German Patent 735,096). Paraffin sulfonates preferably contain 13 to 17 carbon atoms and are usually monosulfates, but may be di-, tri- or higher sulfonates if desired. Di- and polysulfonates are typically used in admixture with the corresponding monosulfate, for example, a mixture of mono- and disulfonates containing about 30% disulfonate. Its hydrocarbon substituent is primarily straight-chain, but if desired, branched-chain paraffin sulfonates can be used, although they are not as good in terms of degradation in nature.

Other suitable anionic detergents include sulfated ethoxylated higher fatty alcohols of formula 12,74731 RO (C2H4O) wherein R is fatty alkyl containing 10-18 or 20 carbon atoms, m is 2-6 or 8 (its value is preferably about 1 / 5-1 / 2 of the number of carbon atoms of the radical R) and M is a solubilizing salt-forming cation such as an early metal, ammonium, lower alkylamino or lower alkanolamino, or a higher alkylbenzenesulfonate in which the higher alkyl contains 10-15 carbon atoms. As is preferred for the nonionic detergent, it is most preferred that the alkyl length of the anionic alkoxylate detergent be a mixture of different chain lengths, such as chains of 11, 12, 13, 14 and 15 carbon atoms or chains of 12 and 13 carbon atoms rather than all the same chain length.

Ethylene oxide is the preferred lower alkylene oxide in an anionic alkoxylate detergent as well as a nonionic detergent and its proportion in the polyethoxylated higher alkanol sulfate is predominantly 2-5 moles of ethylene oxide groups per mole. 15 carbon atoms. To maintain the desired hydrophilic-lipophilic balance when the carbon atom content in the alkyl chain is at the lower end of the carbon atoms range 10-18, the ethylene oxide content of the detergent can be reduced to about two moles per mole, while when the higher alkanol contains 16-18 carbon atoms at the end the number of groups can be increased to four or five and in some cases as high as 8 or 9. Likewise, the salt-forming cation can be changed to achieve the best solubility. It may be any solubilizing metal or radical, but most often it is an alkali metal, for example sodium or ammonium. If Lower alkylamine or alkanolamine groups are used, the alkyls and alkanols usually contain 1 to 4 carbon atoms, and the amines and alkanolamines may be mono-, di- or trisubstituted, such as in monoethanolamine, diisopropanolamine and trimethylamine.

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Polyalkoxyalkoxy-higher alkanol sulfates may be used in place of or in combination with other preferred anionic detergents such as higher alkyl benzene sulfonates to supplement the non-ionic detergent in the liquid detergent compositions in question. One of the preferred polyethoxy alcohol sulfate detergents is available from Shell Chemical Company and is marketed under the name Neodol 25-3 S.

Examples of the invention for use in liquid detergent compositions korkeampialkoholipolyeteenioksisulfaa-compounds are: connected 2_i5 C ^ ^ bellows-normal or primary alkyl trieteenioksisulfaatin sodium salt, potassium salt myristyylitrieteenioksi sulfate, n-dekyylidieteenioksisulfaatin dieta-noliamiinisuola, lauryylidieteenioksisuLfiaähin'a ammoniumsuo-la, palmityylitetraeteenioksisulfaatin sodium salt, a combined C -L4-N-normal primary alkyl-combined sodium salt of tri- and tetraethylene oxysulfate, stearyl pentaethylene oxysulfate trimethylamine salt, and combined potassium salt of C1-7-normal primary prienyl alkyl triethylene oxysulfate.

Countries> useful anionic detergents include higher acyl sarcosinates, for example sodium N-lauroyl sarcosinate, higher fatty alcohol sulphates such as sodium lauryl sulphate and sodium tallow sulphonate sulphate, higher sulphate oils. inferior to polyethoxysulfates, aromatic poly (Al-palkyleneoxy) ether sulfates such as sulfates of condensation products of ethylene oxide and nonylphenol (usually having 1-20, more preferably 2-12 oxyethylene groups per molecule); polyethoxy higher alcohol sulfates and alkylphenol polyethoxysulfates having a lower alkoxy substituent (having 1 to 4 carbon atoms, e.g. methoxy) attached to a carbon atom adjacent to a carbon atom containing a sulfate group, e.g. a mixture of straight chain adjacent alkane diols; acyl esters of isethionic acid, for example oleyl isethionates; acyl N-methyl taurides, for example potassium N-methyl lauroyl or oleyl taurides; higher-alkyylifenyylipolyetoksisulfonaatit; higher alkyl phenyl disulfonates, for example pentadecyl phenyl disulfonate; higher fatty acid soaps, for example combined coconut oil and tallow soaps in a ratio of 1: 4.

Of the anionic detergents of the above type, sulfates and sulfonates are generally preferred, but the corresponding organic phosphates and phosphonates can also be used when the amount of phosphorus they contain is not harmful. Water-soluble anionic organic synthetic detergents (including soaps) are usually, as indicated above, salts of alkali metal cations such as potassium, lithium and especially sodium, although ammonium and substituted ammonium cations may also be used, such as those previously described for triethanolamine and triisopropyl. In the above description of water-soluble anionic detergents, it should be noted that the sodium, potassium, ammonium and alkanol ammonium salts of each detergent are indicated individually.

Ampholytic detergents can be used in the compositions in question in small amounts instead of or in place of an anionic detergent or in place of a part of a nonionic detergent. Ampholytic detergents include higher fatty carboxylates, phosphates, sulfates or sulfonates containing a cationic substituent such as an amino group which can be quaternized, for example with a lower alkyl group, or the chain extended at the amino group by condensation with a lower alkylene oxide, for example. Mixtures containing such ampholytic or cationic detergents are generally less effective and may have a greater tendency to gel or thicken on standing. Therefore, they are often avoided.

But as long as these properties are not detrimental, smaller amounts of ampholytic detergents such as Miranol C2M sold by Miranol Chemical Company or Deriphat 151, sodium N-coconut-6-amine propionate sold by General Mills, Inc. can be used. may sometimes be useful is distearyldimethylammonium chloride (which has a fabric softening effect) and higher fatty amine oxides such as bis- (2-hydroxyethyl) -octadecylamine oxide.

The viscosity control agent used to maintain the desired viscosity in the liquid detergent composition, to prevent gel agglomeration at low temperatures and to reduce the lower alkanol solvent content is preferably a water-soluble formate. Sodium formate is preferred, but other alkali metal formates may be used, such as potassium formate and several other water-soluble formates, as well as formic acid, which may be added to the liquid detergent mixture where it dissolves, ionizes and / or reacts to form substantially the same type of liquid detergent. addition of alkali thallium formate in the form of a salt. Other formates that can be used are those with water-soluble cations as described above as salt-forming cations of anionic detergents. Although it is considered best to use formate as a viscosity regulator, it has been found that several salts of dibasic acids can also be used successfully, and of these, disodium adipate, referred to herein as sodium adipate, has proven to be the best. Other salts of dibasic acids of formula (CH2) niC00H) 2 'wherein n is 1-6 may also be used and in some cases salts of monounsaturated acids of the same chain length and configuration may be used. However, it is definitely preferred to use saturated aliphatic straight-chain compounds having a carboxyl group at the ends.

ie 74731

It is more preferred to use those where n is 3-5, most preferably 4, and where the acid is completely neutralized, but acid salts can also be used.

Dibasic acids that can be used as either mono- or di-salts include malonic, succinic, glutaric, adipic and pimelic acids. An unsaturated dibasic acid, maleic acid, can also be used, at least in part. The acids can be used without prior neutralization or can be used as their salts such as disodium malonate, monopotassium succinate, ditriethanolamine glutarate, disodium adipate and monosodium pimelate.

To promote the solubility of detergents and possibly optical brighteners present in liquid detergent compositions, a small amount of alkaline substance or a mixture of such substances is often added to the recipes in question. Suitable time substances include mono-, di- and trialkanolamines, alkylamines, ammonium hydroxides. Of these, alkanolamines, especially trialkanolamines and especially triethanolamine, are considered to be the best substances. The final pH of a liquid detergent mixture containing such a basic substance is usually neutral or weakly basic.

Good pH ranges are 7-10, preferably about 7.5-9, and most preferably about 7.5-8.5.

Optical fluorescent brighteners or bleaches used in liquid detergent compositions are important ingredients in modern detergent compositions that give washed laundry and materials a clear appearance so that the laundry is not only clean, but also looks clean. Although it is possible to use a single brightener for a particular purpose in the liquid detergent in question, it is usually advantageous to use mixtures of brighteners which have a good brightening effect on cotton, nation, polyesters and mixtures of these materials and which are also bleach resistant. I '74731 optical brighteners of this type are well described in the article "The Requirements of Present Day Detergent Fluorescent Whitening Agents", A.E. Siegrist, J. Am. Oil Chemists Soc., January 1978 (Vol. 55). This article and U.S. Patent 3,812,041 are both incorporated herein by reference in their entirety as they provide relevant information and contain a detailed description of a number of suitable optical brighteners.

The brighteners used in the liquid detergent compositions in question are: Calcofluor 5BM (American Cyanamid); Calcofluor White ALF (American Cyanamid); SOF A-2001 (Ciba); CDW (Hilton-Davis); Phorwite RKH, Phorwite BBH and Phorwite BHC (Verona); CSL, powdered, acid (American Cyanamid); FB 766 (Verona); Blancophor PD (GAF); UNPA (Geigy); Tinopal RBS 200 (Geigy). The acidic or "non-ionic" forms of brighteners are generally soluble under the influence of the alcohols of the recipes in question, while the salts are generally water-soluble.

Additives may be present in the liquid detergent composition to give it additional properties, either functional or aesthetic. Useful additives include e.g. dirt suspending or anti-re-anti-caking agents such as polyvinyl alcohol, sodium carboxymethylcellulose, hydroxypropylmethylcellulose-thickening agents, for example gums, alginates, agar-agar, foaming agents, for example laurine myristinediethanolamide; antifoaming agents such as silicones; bactericides such as tribromosalicylanilide, hexachlorophene; dyes; pigments (water dispersible); preservatives; ultraviolet light absorbing agents; textile softeners; opacifiers such as polystyrene suspensions and perfumes. These materials must, of course, be selected according to the desired properties of the final product and must be compatible with the ingredients of the shape of the product. Other additives that can be used are dihydric or trihydric lower alcohols, which, in addition to being solvents and lowering the flash point of the product, can act as antifreeze agents and can improve the compatibility of the solvent system with some of the ingredients in the product. The most preferred group of these compounds comprises lower polyols having 2-3 carbon atoms, for example ethylene glycol, propylene glycol and glycerol, but lower alkyl (C 1 -C 4) ether derivatives of these compounds, known as Cellosolves, are also suitable. The proportion of these lower alkanol substitutes is limited and is normally considered to be less than 20% of the total alcohol content of the liquid detergent.

Another category of useful additives are hydrotropic agents used to improve the solubility of components in an aqueous solution whose otherwise solubility in water is limited. Useful hydrotropes include the alkali metal, ammonium and ethanolamine salts of the following acids: 1) arylsulfonic acids such as benzenesulfonic acid and C 1 -C 4 alkyl substituted benzenesulfonic acids, for example toluenesulfonic acid and xylenesulfonic acid; and 2) C 1 -C 4 alkyl sulfuric acids such as hexyl sulfuric acid.

The proportions of the various components of the liquid detergent composition in question are important in order to produce a uniform product having the desired viscosity and high washing effect and which does not gel at low temperatures or when standing in an open container at room temperature.

In order to promote the solubility of fluorescent brighteners and other detergent composition ingredients and to obtain a clear, homogeneous and easily pourable liquid product, 10-60 S of the entire liquid detergent concentrate should be a non-ionic detergent. Especially when an anionic detergent is present in the liquid product, the proportion of nonionic detergent is preferably 20-40% and more preferably 30-40%, and in the present best known recipe it is about 32%. The proportion of anionic detergent is typically 3-1531%, preferably 4-12% and most preferably 6-10%, and is currently about 7% in the best known recipe. The ratio of total nonionic detergent to anionic detergent is usually 15: 1 to 1: 1, preferably 8: 1 to 2: 1, and most preferably 5: 1 to 3: 1.

The lower alkanol in the liquid detergent compositions is usually present in an amount sufficient to help dissolve and / or stabilize the various components of the final product. The proportions of lower alkanol used are usually about 3-15%, more preferably 4-12%, and most preferably 4-8%, and currently most preferably about 5%.

The viscosity control agent or mixture of these agents used is usually about 0.5-5% of the final liquid detergent mixture, preferably about 0.5-3% and most preferably about 1%.

The proportion of water, the main solvent of the mixtures in question, is usually about 25-85%, preferably 35-65% and most preferably about 40-55% by weight of the liquid mixture. The best recipes contain about 45-50% water.

The proportion of an alkaline additive such as triethanolamine in the liquid mixture is usually about 0.1-5% of the mixture and mainly 1-3% by weight. The total amount of optical brightener is usually about 0.5-1.5%, preferably about 0.1-1% and most preferably about 0.2-0.5%.

The liquid detergent composition of the present invention can be made by a simple manufacturing technique. In a typical preparation method, optical brighteners are made into a slurry in a monohydric alcohol, followed by the addition of water to the slurry along with a small amount of base such as triethanolamine, which helps to dissolve some of the previously suspended substances. The addition of the anionic detergent compound usually results in the residue of the clarifier dissolving and a clear solution of 74731 20 is formed. The viscosity adjusting agent is then added in the form of an acid, acid salt or fully neutralized salt, mainly a sodium or potassium salt, and stirring is continued until the solution clarifies, which normally takes about 5-10 minutes. At this point, the main detergent, a nonionic, and a minor amount of acid is added to adjust the pH, and the pH is usually adjusted to the value at which the proteolytic enzyme is most stable. This is followed by mixing the solution and adding additives such as perfume and colorant to give the product its final desired properties. The protease and α-amylase enzyme preparations are then added to the solution and mixed with it, which is the last step in the preparation of the liquid detergent mixture product. If desired, a viscosity regulating agent may be added earlier during the process.

The above operations may be carried out at room temperature, although if desired, suitable temperatures of 20 ° to 50 ° C may be used, provided that when volatile substances such as perfume are added, the temperature should be low enough to avoid harmful losses. The pH of the product obtained is usually between 7 and 10 and the density between 0.9 and 1.1, preferably 0.95-1.05. The viscosity of the final product at 24 ° C is in the range of 60-150 cP, preferably about 80-140 cP, and most preferably about 115-135 cP as measured by a Brookfield viscometer at room temperature.

The liquid mixtures in question are effective and easy to use. Compared to high-performance laundry detergent powders, much smaller volumes are used than the liquids in question to obtain a similar degree of cleanliness of the laundry. For example, using the typical preferred recipe of this invention, only about 60 g, or 1/4 cup, of liquid is needed for a full wash tank of a top-loading washing machine with a water volume of 55-75 liters, and even less (about 1/2) is needed for front-loading machines. The concentration of the liquid detergent mixture in the washing water is then in the order of about 0.1%. The proportion of liquid mixture in the washing solution is usually about 0.05-0.3%, preferably 0.08-0.2% and most preferably about 0.1-0.15%. The amounts of the other various ingredients of the liquid mixture may vary as well. Equivalent results can be obtained using larger amounts of a more dilute prescription, but the larger amount required requires additional packaging and is usually more difficult for the consumer to use. Highly diluted products are also more susceptible to freezing in cold climates and more susceptible to hydrolysis and chemical changes during storage.

Example 1

A liquid detergent composition (free of enzymes) was prepared, designated mixture "A" at room temperature, by mixing the following ingredients in the indicated proportions:

Ingredient Weight%

Primary ethoxylated C12-c155 al-ol 32.0 (7 moles EO / mole alcohol)

Sodium dodecylbenzenesulphonate 7.0

Triethanolamine 2.8

Ethanol 5.0

Sodium formate 1.0 H 2 SO 4 (conc.) 0.7

Optical brightener ^ q 27 .... (2) Dye 0.01

Perfume 0.35

Water remainder ^ Mixture of Phorwite RKH and Phorwite EHC brighteners, manufactured by Verona.

Polar Brilhant Blue (PBB), manufactured by Ciba-Geigy.

(2) 22 7 4 7 31

Enzyme-containing liquid detergent compositions B to U were formulated by adding various large amounts of protease and α-amylase enzymes to mixture A described above. The enzyme concentration in each detergent composition is shown in Table 1 and is expressed as a percentage of the weight of the enzyme preparation. The protease enzyme used was a liquid enzyme preparation sold under the name "Alcalase", manufactured by Novo Industries, Copenhagen, Denmark, at a concentration of 2.5 Anson units per gram of enzyme preparation. The α-amylase enzyme used was a liquid enzyme preparation sold under the name "Termamyl" by Novo Industries at a concentration of 120,000 Novo amylase units per gram of liquid enzyme preparation.

test procedure

A total of 6 cotton swabs, 3 stained with bovine liver blood and 3 stained with grass, were placed in each of four buckets of a Tergotometer manufactured by U.S. Pat. Testing Company. A series of laundry tests were performed using different liquid detergent mixtures from mixtures A-U in each bucket of the Tergotometer under the following test conditions:

Liquid detergent concentration 0.09%

Mixing at 100 rpm

Mixing time 10 min

Water temperature 49 ° C

Water hardness about 150 ppm as calcium carbonate

After washing, the test patches were rinsed in tap water and then dried. The stain removal percentage was calculated by taking a reflection reading from each stained test tag before and after washing using a Gardner XL-20 Colorimeter and the stain removal percentage (% SR) was calculated as follows:% SR = after washing) - (Rd before washing) (Rd before staining) - (Rd before washing) ) 23 74 731 where "Rd before washing" means Rd after staining.

From each of the three test patches with the same stain, the calculated stain removal percentages were averaged for each liquid detergent composition tested. The results are shown in Table 1, which shows the S.R.% of each of the liquid detergent mixtures tested (mixtures A-U) and the enzyme concentration of such detergent mixtures.

table 1

Comparative stain removal using detergent mixtures containing enzymes

Weight% ... Weight% ^ strip removal-l

Mixture protease α-amylase blood Grass A 0.0 0.0 42.0 31.5 B 0.2 0.0 50.8 37.6 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 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 U 0.0 0, S 47.7 36.5 ^ The proteolytic effect of Alcalase is 2.5 Anson units per gram. Thus, for example, a concentration of 0.2% Alca in a liquid detergent composition corresponds to the effect of a protease enzyme of 0.5 Anson units (0.2 x 2.5) per 100 g of detergent composition.

24 74731 (2)

The amylolytic effect of termamyl is 120,000 Novo Amy glass units per gram. Thus, a concentration of 0.2% Termamyl in the liquid detergent mixture corresponds to the effect of the enzyme α-arnylase 24,000 Novo-amylase units (0.2 x 120,000) per 100 g of the detergent mixture.

As indicated in Table 1, the stain removal percentage (S.R.) obtained with the mixture A, S.R., represents the value obtained with the detergent mixture without enzymes. Comparing the SR data for bovine liver blood obtained with mixtures of FK P and U, all of which contain amylase enzyme but are not protease and are therefore not in accordance with the invention, it is found that mixture P containing 0.6% by weight of -amylase gave the maximal improvement in SR (47%) available with the enzyme amylase, i.e. an increase of about 5.7% relative to the SR value of 42.0% with enzyme-free mixture A. Similarly, a comparison with mixtures B, C, D and E, all containing protease enzyme but not amylase, shows that the SR values obtained with mixture obtained containing 0.8% protease, the maximum increase in SR (55 S) by the protease enzyme, i.e. about 13.5% relative to 42% S.R. obtained with enzyme-free mixture A.

Table 1 clearly shows the synergistic interaction of protease and amylase enzymes in the removal of proteinaceous stains. Thus, for example, a mixture G containing 0.2% by weight of protease and 0.2% by weight of amylase (corresponding to a ratio of amylase / protease enzyme effects of 24,000 Novo amylase units per 0.5 Anson units) gave almost the same SR: n improvement (calculated from enzyme-free mixture A) to obtain 0.8% by weight of protease in mixture E. From an economic point of view, the use of mixture G containing the enzyme mixture according to the invention clearly represents a significant reduction in the need for relatively expensive protease enzyme compared to mixture E.

25 7 4 7 31

The highest percentage of stain removal was obtained with mixture N. In particular, the combination of 0.6% by weight of protease and 0.4% by weight of amylase in mixture N gave an increase of more than 21% in SR relative to blood stain, calculated from enzyme-free mixture A. 63.3 % SR is thus significantly higher than the maximum S.R. that could be obtained with detergent compositions containing a protease enzyme and no α-amylase at all. The amylase / protease enzyme activity ratio of such a mixture is 48,000 Novo amylase units per 1.5 Anson units.

The synergistic interaction of protease and alpha-amylase enzymes is also evident in the S.R. data obtained with grass stains. For example, mixture H, which contained 0.2% Amylase and 0.4% protease enzymes, gave a significantly higher S.R. value than could be obtained with detergent compositions containing either protease or amylase as individual enzymes in the mixture.

Claims (6)

1. Enzyme-containing liquid detergent composition for use in textile washing, characterized in that it contains S11s: (a) about 5-75% by weight of one or more surfactant detergents selected from the group consisting of anionic, nonionic, cat. ionic, ampholytic and an amphoteric ion containing compounds: (b) about 0.5-5% by weight of a viscosity regulating agent selected from the group consisting of water-soluble formate salts and dihydric acids of formula (CH) (C00H); where n is 1-6, 2 n 2 * (c) about 25-85% of the wetting; and (d) an enzyme mixture containing substantially the same protease enzyme and the amylase enzyme in such conditions that the ratio of the effects of the enzymes in said mixture is about 4000 - about 80,000 Novo-amylase units of alpha-amylase per Anson units of protease, and said protease is presently very much so that per 100 g of detergent composition there are about 0.25 - about 2.5 Anson units. Detergent composition according to claim 1, characterized in that the ratio of enzyme effects in said enzyme mixture is about 15,000 - about 40,000 Novo-amylase units of alpha-amylase per Anson units of protease, and said protease is presently one side amount, that per 100 g of detergent composition contains about 0.5 - about 2.0 Anson units. Detergent composition according to claim 2, characterized in that said ratio of the enzyme effects is about 30,000 - about 40,000 Novo-amylase units of alpha-amylase per Anson units of protease. 4. Detergent composition according to claim 1, characterized in that said surfactant detergent mainly contains about 20 - about 40% by weight of water-soluble C and about 4-12% by weight of the water-soluble C , lower polyol having 2-3 carbon atoms and their mixtures. Detergent composition according to claim 1, characterized in that it further contains 0.1-5% by weight of alkanolamine. 6. Detergent composition according to claim 1, characterized in that said nonionic detergent compound is a polyethoxylated C 1-6 alkanol having 3-12 ethylene oxide groups per mole; said anionic detergent is a C or C 13 alkyl benzenesulfonate; said lower alkanol is ethanol or a mixture of ethanol and isopropanol; and said viscosity controlling agent is sodium formate.