SE460726B - ENZYMINE-CONTAINING LIQUID DETERGENT PREPARATION AND ITS APPLICATION IN HOUSHAALLSTWETT - Google Patents

Description

460 726 k) Detergent preparations containing enzyme mixtures, e.g. proteases and amylases, have been extensively described in the literature. For example, U.S. Patent 3,630,930 discloses a granular detergent composition containing from about 0.5 to 20 2 enzyme-bearing granules which comprise from about 0.00l to 10% mixtures of protease and amylase enzymes in a weight ratio of 50: 1 to 1: 5 between protease and amylase.

British Patent 1,240,058 discloses a granular detergent composition containing a mixture of protease and amylase enzymes having a weight ratio of protease to amylase of 30: 1 to 3: 1, the weight percent of amylase in the formulation being from 0.0003 to 3 %.

U.S. Patent 3,931,034 to Inamorator et al discloses a granular detergent composition containing a mixture of alkaline protease enzyme and β-amylase enzyme in an activity ratio ranging from 100,000 to 400,000 Novo-amylase units of amylase per Anson unit of protease.

Although the use of enzyme mixtures in granular detergent compositions is generally described in the patent literature, in most cases the mixtures themselves are so widely described that they include, for example, mixtures in which the percentage of protease may vary within a range of five orders of magnitude (British Patent 1,240,058 ), or in which the percentage of amylase can vary within a range of five orders of magnitude (U.S. Patent 3,630,930), leading to a presumption that if a larger amount of enzyme is used within these wide ranges, stain removal becomes more efficient. In addition, the above-mentioned patents, as well as the Inamorato patent, are strictly limited to granular formulations and thus provide no instruction for the use of enzyme mixtures in liquid formulations. The present invention provides an enzyme-containing liquid detergent composition comprising; (a) from about 5% to about 75% by weight of one or more detergent surfactants selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergent compounds; (b) from about 25% to 85% by weight of water; and (c) an enzyme mixture consisting essentially of an alkaline protease enzyme and a β-4-amylase enzyme is characterized in that the protease enzyme and the α-β-amylase enzyme are present in such relative proportions that the ratio of respective enzyme activities in this mixture is from about 4,000 to about 80 000 Novo-amylase units of 4-amylase per Anson unit of protease, which protease is present in an amount giving from about 0.25 to about 2.5 Anson units per 100 g of detergent preparation.

Embodiments of the invented formulation are set out in claims 2 to 10.

In accordance with the method according to the invention, household washing of stained and / or soiled materials is carried out by contacting these materials with an aqueous solution of the above-mentioned liquid detergent formulation.

The present invention is based on the discovery that the amount of alkaline protease enzyme normally required for the removal of proteinaceous stains can be significantly reduced by combining it with an amount of amylase enzyme according to the invention, so as to obtain a detergent composition having equivalent or improved stain removal ability. with a significantly reduced cost for the constituent components. Unlike 460 726 from the description in the literature which recommends that proteases and amylases be mixed within wide ranges in detergent compositions, the enzyme mixture described herein is characterized by a synergistic interaction between protease and amylase, and comprises only those mixtures which have a narrowly defined activity ratio. .

The activities of the alkaline protease enzyme and the olamylase enzyme are expressed in Anson units for protease and Novo-amylase units for amylase, respectively. These are units commonly used in the art to describe under ordinary conditions the activity of enzyme preparations containing protease or amylase enzymes.

In a preferred embodiment of the invention, the enzyme mixture contains relative amounts of alkaline protease and Novo-amylase units of α-amylase which yield from about 10,000 to 50,000 DL-amylase per Anson unit of protease, with an activity ratio of from about 1,000 to 40,000 is even more preferred, and a ratio of from about cially desirable.

The amount of enzyme mixture that the detergent composition will, of course, in some .000 to 40,000 is in the liquid to a large extent depends on the amount of preparation to be added to the detergent solution. intended for use in concentrations of about 0.15%. For detergent in the washing solution in an automatic household washing machine, a suitable amount of mixture will give from about 0.25 to about 2.5 Anson units of protease per 100 grams of detergent formulation, ratio of from about and with about 1.5 Anson with a 0.5 to 2.0 being preferred, units per 100 g of formulation 460,726 is a particularly preferred protease concentration.

Detailed Description of the Invention The activity of the alkaline protease enzyme is measured as previously mentioned in Anson units. The Anson hemoglobin method for measuring the activity of Anson units is a method well known in the art for indicating the activity of proteolytic enzymes, and is described in "Journal of General Physiology", Volume 22, p. 79 - 89 (1939), the disclosure of which is incorporated herein by reference. The modified Anson hemoglobin method can also be used to measure the proteolytic activity, which modified method is described in the article "Alkali-Resistant Enzyme for Detergents", SR 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 digest a denatured hemoglobin substrate under standardized conditions in a buffered aqueous medium at the selected pH, and the amount of molten material is determined by a staining test with a phenolic reagent.

The activity of the ° 4-amylase enzyme is measured as previously mentioned in Novo-amylase units. The standard method for measuring these Novo units is a modification of the SKB method (Sandstedt, Kneen & Blish, Cereal Chemistry 16, 712, (1939)) without the addition of beta-amylase. in this method, 20 ml of buffered starch solution (prepared by the method described below) are measured in a test tube (diameter 24 mm, length l90 mm) and placed in a water thermostat having a temperature of 370 C. After a few minutes of preheating add 10 ml of the amylase solution (or v ml of amylase solution + (10-v) ml of water) to the test to be tested, mix the contents of the tube thoroughly and start at the same time for 1 hour. At appropriate time intervals, add 1 ml of the reaction mixture. to 5 ml of dilute iodine solution (prepared according to the method described below) and shaken and transferred to a control tube, and the color is compared with the color standard.If the end point of staining is reached after less than 10 minutes, use a more dilute amylase solution or a smaller volume amylase solution.

A Holy Comparator 607 was used as a colorimeter in conjunction with the glass-0 <-amylase standard (compare Redfern Methods for Determination of Ethyl Amylase, Cereal Chemistry gi, 259 (1947)). The 04-amylase activity of the sample can be calculated by the following formula: A = 1430 x V txaxv which 1 = the G.-amylase activity in Novo-amylase units per gram = time to reach the end point of the staining (minutes) 4 (weight of the sample in grams (= the volume to which the sample is diluted (ml) i = the volume of the amylase solution used (ml) \ The above "dilute iodine solution" is prepared by dissolving 1 ml of "iodine stock solution" and 20 g of potassium iodide in sufficient water to give 500 ml; 460 726 The "iodine stock solution" is prepared by dissolving 11 g of iodine crystals and 22 g of potassium iodide in sufficient water to give 500 ml. The above-mentioned "buffered starch solution" is prepared as follows: 10 g of soluble starch (eg Merck, Amylum solubile, Soluble Starch, Brgl B.6) calculated as a dry substance are transferred to a slurry by means of a little water. The slurry is added to about 200 ml of boiling water. When the starch is completely dissolved, the solution is cooled and transferred to a one-liter volumetric flask, after which the water is made up to the mark. The starch solution (made by dissolving 9.36 g Naci, 69.00 q KHZPO4, 4.80 g Na2néo4, 2 nzo in sufficient water to give one liter. Finally, saturate the solution with toluene. The pH of the final buffered starch solution should be 5.7. The starch solution must be as fresh as possible but can be stored in a refrigerator for a maximum of 24 hours. Distilled water is used in all cases.

The enzyme activity of proteolytic and amylolytic enzyme preparations is generally determined for practical reasons without carrying out the assay procedure described above. The enzyme activity is reported by the manufacturers for most commercially available liquid enzyme preparations containing protease or amylase enzyme, and is expressed in Anson units, or Novo-amylase units (or in units directly proportional thereto). Alternatively, the activity of a given enzyme preparation can be readily determined analytically by a method in which the enzyme reactivity of a protein or starch substrate can be measured under standard conditions and then compared with the reactivity of enzyme preparations with known activity for reference. In these analytical methods, the enzyme activity is conveniently expressed x 460 726 as the optical density measured under standard conditions of a sample solution containing the enzyme preparation and the protein or starch substrate, a high optical density corresponding to high activity.

Suitable alkaline proteolytic enzymes include the various commercial liquid enzyme formulations which have been adapted for use in detergent formulations, powdered enzyme formulations also being useful, although they are generally less suitable for incorporation into the present liquid detergent formulations. Suitable liquid enzyme formulations thus include "Alcalase" and "Esperase" sold by Novo Industries, Copenhagen, Denmark, and "Maxatase" and "AZ-Proteas" sold by Gist-Brocades, Delft, The Netherlands. "Alcalase" is particularly preferred for the available preparations.

Suitable liquid ml-amylase enzyme preparations are those sold by Novo Industries and Gist-Brocades under the trade names "Termamyl" and "Maxamyl".

Preferably, an organic solvent is used together with water, to serve as a solvent for the liquid detergent preparation. The preferred organic solvent is a lower alkanol having 1 to 4 carbon atoms, and having 1 to 3 hydroxy groups, preferably 1 or 2. The lower alkanol is preferably ethanol or a mixture of ethanol and isopropanol, however, lower monohydric alcohols such as propanol and butanol, and lower polyols having 2 to 3 carbon atoms such as ethylene glycol and propylene glycol are useful but less preferred. Use of primary, secondary and tertiary butanol or n-propanol as the lower alkano- i; w.

I | .MT-g \, ...._ / \ * and organic solvent. Mixtures of ethanol and 460,726 len are generally limited to mixtures thereof with ethanol, ethanol preferably constituting at least 80 to 90% of these mixtures. It is highly preferred to use ethanol as the sole alkanol isopropanol, it is preferred that ethanol constitute the main constituent, the ethanol usually constituting from 60 to 90% of the mixture, preferably about 75% (i.e. in the ratio 3: 1). Of course, other mixtures of the different alkanols can be used, e.g. ethanol and propylene glycol, and even in these mixtures it is preferred to have ethanol as the main ingredient. The formulations of the present invention contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic and zwitterionic 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 described in detail in the publication Surface Active Agents, Vol. II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, the relevant content of which is incorporated herein by reference. The nonionic detergents are usually poly-lower alkoxylated lipophils in which the desired hydrophilic-lipophilic balance is achieved by adding a poly-lower alkoxy group to a lipophilic residue. In the present formulations, the nonionic detergent used is preferably a poly-lower alkoxylated-higher alkanol in which the alkanol has 10 to 18 carbon atoms and in which the number of moles of lower alkylene oxide (having 2 or 3 carbon atoms) is from 3 to 12. Among 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 which contains from 5 to 8 or 5 to 9 lower alkoxy groups per mole. The lower alkoxy group is preferably ethoxy but in some cases it is desirable to mix it with propoxy, the latter usually being included in a lower proportion (less than 50%). Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, e.g. Neodol 25-7 and Neodol 23-6.5, which products are manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols with an average of about 12 to 15 carbon atoms with about 7 moles of ethylene oxide, and the latter is a corresponding mixture in which the higher fatty alcohol contains 12 to 13 carbon atoms and the number of ethylene oxide groups per mole is on average about 6.5. The higher alcohols are primary alkanols. Other examples of such detergents include Tergitolgglš-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates manufactured by Union Carbide Corporation. The former is a mixed ethoxylation product of a linear secondary alcohol having 11 to 15 carbon atoms and 7 moles of ethylene oxide, and the latter is a similar product with 9 moles of ethylene oxide. Higher molecular weight nonionic agents are also useful in the present formulations, e.g. Neodol 45-1, which are similar condensation products of ethylene oxide and higher fatty alcohols, wherein the higher fatty alcohol has 14 to 15 carbon atoms and the number of ethylene oxide groups per mole is about 11. These products are also manufactured by Shell Chemical Company. Other useful nonionic «460 726 ll agents may be represented by Plurafac B-26 (BASF Chemical Company), which is a reaction product of a higher linear alcohol and a mixture of ethylene oxide and propylene oxide.

In the preferred poly-lower alkoxylated-higher alkanols, the best balance between hydrophilic and lipophilic residues is obtained when the number of lower alkoxy is from about 40 till to 100% of the number of carbon atoms in the higher alcohol, and preferably is from 40 to 60% of these. The nonionic detergent preferably comprises at least 50% of the preferred ethoxylated alkanols. Higher molecular weight alkanols and various other, normally solid, nonionic detergent compounds and surfactants can contribute to gel formation in the liquid detergent formulation, and are normally excluded or limited in the present formulations, although smaller proportions of these may be used due to their cleaning properties, etc. Both in the case of the preferred and less preferred nonionic detergents, the alkyl groups contained therein are preferably linear, although a minor degree of minor branching can be accepted, e.g. at a carbon adjacent to, or at a distance of two carbons from, the terminating carbon in the straight chain and facing away from the ethoxy chain, provided that this branched alkyl is not longer than three carbon atoms. The proportion of carbon atoms in such a branched configuration is normally small, and rarely exceeds 20% of the total carbon content of the alkylene.

Although linear alkyls terminally linked to ethylene oxide chains are highly preferred and are considered to provide the optimal combination of cleaning, biodegradable and non-gelling properties, middle bonding and secondary bonding with the ethylene oxide in the chain can also occur. In these cases it is usually only in a small proportion of these alkyls, generally less than 20%, but can e.g. as regards the previously mentioned .Tergitols be larger. Even when propylene oxide is included in the lower alkylene oxide chain, it is usually less than 20% of this and preferably less than 10%.

An anionic detergent may be used in conjunction with the nonionic detergent which is the major synthetic organic detergent in the present liquid detergent formulations. The most preferred anionic detergent compounds are the higher (10 to 18 or 20 carbon atoms) alkylbenzenesulfonate salts wherein the alkyl group preferably contains 10 to 15 carbon atoms, and most preferably is 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 isomers and a correspondingly low content (usually well below 50%) of 2- (or lower) phenyl isomers; in other words, the benzene ring is preferably largely attached in the 3, 4, 5, 6 or 7 position to the alkyl group and the content of isomers in which the benzene ring is attached in the 1 or 2 position is correspondingly low. Typical alkylbenzenesulfonate surfactants are described in U.S. Patent 3,320,174. Of course, even more highly branched alkylbenzenesulfonates may be used, but are generally not preferred due to lack of biodegradability.

Olefin sulfonate salts are other anionic detergents that can be used. These generally contain long chain alkenyl sulfonates or long chain hydroxyalkane sulfonates (the hydroxy group being attached to the carbon atom which is not attached directly to the carbon atom bearing the SO 3 H group). The olefin sulfonate detergent typically comprises a mixture of varying amounts of these types of compounds, often together with long chain disulfonates or sulfate sulfonates. Such olefin sulfonates are described in many patents, e.g. in the U.S. Patents 2,061,618, 3,409, 637, 3,332,880, 3,420,875, 3,428,654, 3,506,580 and in British Patent 1,129,158. The number of carbon atoms in the olefin sulfonate is usually in the range of 10 to 25, and most often l0 to 18 or 20, e.g. a mixture mainly of C12, C14 and C16, with an average of about 14 carbon atoms, or a mixture mainly of C14, C16 and C18 with an average of about 16 carbon atoms.

Another group of anionic detergents is that consisting of higher paraffin sulfonates. These may consist of primary paraffin sulfonates made by reacting long chain alpha-olefins and bisulfites, e.g. sodium bisulfite, or of paraffin sulfonates having the sulfonate groups distributed along the paraffin chain, e.g. products made by reacting a long-chain paraffin with sulfur dioxide and oxygen in ultraviolet light, followed by neutralization with sodium hydroxide or other suitable base (as in U.S. Patents 2 SO3 280, 2,507,088, 3,260,741, 3,372,188 and in German patent 735,096). The paraffin sulfonates preferably contain from 13 to 17 carbon atoms and are normally a monosulfonate but may, if desired, be di-, tri- or higher sulfonates. The disulfonates and polysulfonates are typically used in conjunction with a corresponding monosulfonate, for example in the form of a mixture of mono- and disulfonates containing up to about 30% disulfonate. The hydrocarbon substituent in these is preferably linear, but if desired, branched chain paraffin sulfonates can be used, although they are not as good in terms of biodegradability. 460 726 '. Other suitable anionic detergents are sulfated ethoxylated higher fatty alcohols of the formula RO (C 2 H 4 O) mSO 3 M, in which R is a fatty alkyl having from 10 to 18 or 20 carbon atoms, m is from 2 to 6 or 8 (preferably has a value from about 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 alkylbenzene sulfonate in which the higher alkyl has 10 to 15 carbon atoms . In the same way as with the preferred nonionic detergent, it is preferred that the alkyl in the anionic alkoxylated detergent be a mixture of different chain lengths, e.g. l1, 12, 13, l4 and l5 carbon atoms in the chains or l2 and l3 carbon atoms in the chains, instead of all having one and the same chain length.

Ethylene oxide, like the nonionic detergent, is the preferred lower alkylene oxide of the anionic alkoxylated detergent, and the proportion thereof in the polyethoxylated higher alkanol sulfate is preferably 2 to 5 moles of ethylene oxide groups per mole of anionic detergent, with 3 moles is most preferred, especially when the higher alkanol has 11 or 12 to carbon atoms. To maintain the desired hydrophilic-lipophilic balance when the carbon atom content of the alkyl chain is in the lower part of the 10-18 carbon atom range, the ethylene oxide content of the detergent can be reduced to about two moles per mole, while when the higher alkanol has 16 to 18 carbon atoms and is in the higher part of the range, the number of ethylene oxide groups can be increased to 4 or 5 and in some cases to as high as 8 or 9. The salt-forming cation can also be shifted to obtain the best solubility. It can be any solubilizing metal or radical but is usually a .7 777 'in w 7 í- * a- í V 460 726 alkali metal, e.g. sodium, or ammonium. If lower alkylamine groups or alkanolamine groups are used, the alkyls and alkanols usually contain from 1 to 4 carbon atoms and the amines and alkanolamines may be mono-, di- and tri-substituted, as in monoethanolamine, diisopropanolamine and trimethylamine.

Poly-lower alkoxy-higher alkanol sulfates may be used in place of or in combination with other preferred anionic detergents, e.g. the higher alkylbenzene sulfonates, to supplement the nonionic detergent in the present liquid detergent compositions.

A preferred polyethoxylated alcohol sulfate detergent is available from Shell Chemical Company and is marketed as Neodol 2 §-38. Examples of higher alcohol-polyethyleneoxy sulfates that may be used in the liquid detergent compositions of the invention include: mixed C1-25 normal or primary alkyltriethene oxysulfate sodium salt; myristyl triethylene oxysulfate potassium salt; n-decyl-diethenoxy-sulfate diethanolamine salt; lauryl diethene oxysulfate ammonium salt; palmityltetraethene oxysulfate sodium salt; mixed C14-5 normal primary alkyl mixed tri- and tetraethylene oxy sulfate sodium salt; stearyl pentaethene oxysulfate trimethylamine salt; and mixed C10-18 normally primary alkyl triethylene oxysulfate potassium salt. Other suitable anionic detergents include the higher alkyl sarcosinates, e.g. sodium N-lauroyl sarcosinate; higher fatty alcohol sulphates, e.g. sodium lauryl sulfate and sodium tallow alcohol sedate; sulfated oils; sulfates of mono- or diglycerides of higher fatty acids, e.g. stearin monoglyceride monosulfate; although of these 460 726 l6, sodium higher alcohol sulphates have been found to be inferior to the polyethoxylated sulphates in terms of washing power; aromatic poly (lower alkenoxy) ether sulfates, e.g. the sulfates of the condensation products between ethylene oxide and nonylphenol (usually with 1 to oxyethylene groups per molecule, preferably 2 to 12); polyethoxy higher alcohol sulfates and alkylphenol polyethoxy sulfates having a lower alkoxy (having 1 to 4 carbon atoms, eg methoxy) substituent on a carbon close to that bearing the sulfate group, such as monomethyl ether monosulfate of a long chain vicinal glycol , e.g. a mixture of vicinal alkanediols having 16 to 20 carbon atoms in a straight chain; acyl esters of isethionic acid, e.g. oleyl isethionates; acyl-N-methyl taurides, e.g. potassium N-methyllauroyl or oleyl taurides; higher alkylphenyl polyethoxy sulfonates; higher alkylphenyl disulfonates, e.g. pentadecylphenyl disulfonate; and higher fatty acid soaps, e.g. mixed coconut oil and tallow soaps in a ratio of 1: 4.

The sulfates and sulfonates are generally the preferred among the above types of anionic detergents, but the corresponding organic phosphates and phosphonates may also be used when their phosphorus content can be accepted. In general, the water-soluble anionic synthetic organic detergents (including soaps) previously mentioned are salts of alkali metal cations, such as potassium, lithium and especially sodium, although salts of ammonium and substituted ammonium cations may also be used, as previously described, e.g. . triethanolamine and triisopropylamine. In the above exemplifications of water-soluble anionic detergent, it can be noted that the sodium, potassium, ammonium and alkanolammonium salts are listed individually for each detergent. Smaller proportions of ampholytic detergents may be used in the present formulations as a replacement for the anionic detergent or a portion thereof or as a replacement for a portion of the nonionic detergent.

Ampholytic detergents include higher fat carboxylates, phosphates, sulfates or sulfonates which contain a cationic substituent such as an amino group, which may be quaternized, e.g. with a lower alkyl group, or be chain extended at the amino group by condensation with a lower alkylene oxide, e.g. ethylene oxide.

Compositions containing these ampholytic or cationic detergents are generally less effective and may have an increased tendency to gel or thicken when allowed to stand. That is why they are often avoided. However, if these properties do not interfere, smaller proportions of ampholytes such as Miranol C2M, sold by Miranol Chemical Company, or Deriphat 115, which is a sodium N-coconut beta-amine propionate sold by General Mills, Inc. can be used. detergent which is sometimes useful is distearyldimethylammonium chloride (it has a textile softening effect), as well as the higher fatty amine oxides, such as bis- (2-hydroxyethyl) octadecylamine oxide.

The viscosity control agent used to maintain the desired viscosity of the liquid detergent formulation, to prevent gel formation at low temperatures and to allow a lowering of the lower alkanol solvent content, is preferably a water-soluble form. Sodium format is preferred but alkali metal formats can be used, e.g. potassium formate and various other water-soluble formats, including formic acid which can be added to the liquid detergent composition and dissolved therein, ionized and / or reacted to form substantially the same kind of liquid detergent obtained by the addition of alkali metal formate in form of salt. Other formats that can be used are those derived from water-soluble cations, which have previously been described as salt-forming cations for the anionic detergents. Although it is preferred to use formats as viscosity regulators, it has been found that various salts of dibasic acids can also be used successfully, among which disodium adipate referred to herein as sodium adipate appears to be the best. Other salts of dibasic acids of the formula (CH2) n (COOH) 2 wherein n is 1 to 6 can also be used and in some cases salts of monounsaturated acids can be used, with the same chain length and configuration. However, it is highly preferred to use the saturated aliphatic straight chain terminally carboxylated compounds. It is even more preferred to use those in which n is 3 "to 5, preferably 4, and in which the acid is completely neutralized, but the acid salts can also be used.

Malonic acid, succinic acid. Glutaric acid, adipic acid and pimelic acid are among the dibasic acids that can be used, either as monosalts or disalts. An unsaturated dibasic acid, maleic acid, can also be used, at least to some extent. The acids can be used without prior neutralization or can be used in the form of their salts, such as disodium malonate, monopotassium succinate, di-triethanolamine glutarate, disodium adipate and monosodium pimelate.

In order to assist in the solubilization of the detergents and optical brighteners which may be included in the liquid detergent composition, a small proportion of alkaline material or a mixture of such materials may often be included in the present formulations. Suitable alkaline materials include mono-, di- and tri-alkanolamines, alkylamines and ammonium hydroxides.

The alkanolamines are the preferred materials among them, especially the trialkanolamines and among them especially triethanolamine. The pH value of the final liquid detergent composition containing such a basic material will normally be neutral or slightly basic. Suitable pH ranges are from 7 to 10, preferably from about 7.5 to 9, and most preferably from about 7.5 to 8.5.

The optical fluorescent bleaches or bleaches used in the liquid detergent formulations are important ingredients in modern detergent formulations which give household laundry and other washed materials a bright appearance so that the laundry, in addition to being clean, also looks clean. Although it is possible to use a single bleach for a specific purpose in the present liquid detergent, it is generally desirable to use blends of bleach which have a good whitening effect on cotton, nylon, polyesters and mixtures of such materials and which are also stable to bleaching. A good description of this kind of optical brightener is given in the article "The Requirements of Present Day Detergent Fluorescent Whitening Agents" by A. E. Siegrist, J. Am. Oil Chemists_ Soc., January 1978 (vol. 55). This article and U.S. Patent 3,812,041, issued May 21, 1974, the relevant parts of which are incorporated herein by reference, contain detailed descriptions of a wide variety of optical brighteners.

Among the whitening agents useful in the present liquid detergent compositions may be mentioned: Calcofluor SBM (AmericanCyanamide); Calcofluor White ALF (American Cyanamid); SOF A-2001 (Ciba); CDW (Hilton-Davis); 460 726 A Q 1 Phorwite RKH, Phorwite BBH and Phorwite BHC (Verona); CSL, powder, acid (American Cyanamid), FB 766 (Verona); Blancophor PD (GAF); UNPA (Geigy); Tinopal RBS 200 (Geigy). The acid forms or the "nonionic" forms of the whitening agents tend to be solubilized by alcohols of the present formulas, whereas the salts tend to be water soluble.

Adjuvants may be included in the present liquid detergent composition to provide additional properties, either functional or aesthetic. The useful adjuvants include soil suspensions. agents or antifoulants, such as polyvinyl alcohol, sodium carboxymethylcellulose, hydroxypropylmethylcellulose, thickeners, e.g. rubber binders, alginates, agar-agar; foam improvers, e.g. lauric myristine diethanolamide; foam breakers, e.g. silicones; bactericides, e.g. tribromosalicylanilide, hexachlorophene; dyes; pigments (water-dispersible): preservatives, ultraviolet absorbents; textile softeners; covering agents, e.g. polystyrene suspensions; and perfumes. These substances must, of course, be selected taking into account the desired properties of the final product and so that they are compatible with the other constituents thereof. Dihydric and trivalent lower alcohols are other useful adjuvants which, in addition to being solvents, and which can reduce the flash point of the product, can act as antifreeze agents and can improve the compatibility of the solvent system with special product components. The most preferred K group of these compounds comprises lower polyols having 2 to 3 carbon atoms, e.g. ethylene glycol, propylene glycol and glycerol, but the lower alkyl (C1-C4) ether derivatives of these compounds, known as Cellosolves, can also be used. The proportion of such substitutes for the lower alkanols shall be limited and shall not normally exceed 20% of the total alcoholic strength of the liquid detergent1. Hydrotropes are another category of suitable additives which have the function of improving the solubility of aqueous solution. constituents which otherwise have limited water solubility. Useful hydrotropes are alkali metal, ammonium and ethanolamine salts of the following acids: (1) arylsulfonic acids, such as benzenesulfonic acid and NO1-§3: alkyl-substituted benzenesulfonic acids, e.g. toluenesulfonic acid and xylene sulfonic acid; and (2) C 5 -C 6 alkyl sulfuric acids, such as hexyl sulfuric acid.

The proportions of the various constituents in the present liquid detergent formulations are important for obtaining a uniform product with the desired viscosity and acceptable high-performance washing effect, and which do not form a gel at low temperatures or when stored in an open container at room temperature. .

In order to promote the solubility of the fluorescent whitening agents and other constituents of the detergent preparation and to obtain a clear, homogeneous and easily durable liquid product, from 10 to 60% of the whole liquid detergent concentrate should consist of nonionic detergent. Preferably, and especially when an anionic detergent is included in the liquid product, the proportion of nonionic detergent is from 20 to 40% and more preferably 30 to 40%, with the currently known best composition containing about 32%.

The proportion of anionic detergent is usually in the range 3 to 15%, preferably 4 to 12% and most preferably 6 to%, the currently known best composition containing about 7%. The total proportion of nonionic detergent in relation to the proportion of anionic detergent is normally from 1.5: 1 to 1: 1, with 8: 1 to 2: 1 being preferred and 5: 1 to 3: 1 being most preferred.

The lower alkanol in the liquid detergent formulations is generally included in a sufficient amount to assist in the dissolution and / or stabilization of the various constituents of the final product. The proportion of lower alkanol is normally from about 3 to 15%, preferably 4 to 12%, more preferably 4 to 8% and currently most preferably about 5%.

The proportion of viscosity control agents or mixture of such agents is normally from about 0.5% to 5% of the final liquid detergent composition, preferably about 0.5 to 3%, and most preferably about 1%.

The percentage of water, which is the main solvent in the present formulations, is usually from about zs to es s, preferably as to es% and most preferably from about 40 to 55%, by weight of the liquid formulation. The most preferred compositions contain about 45 to 50% water.

The proportion of alkaline additive, such as triethanolamine, in the liquid detergent formulation is usually from about 0.1 to 5% of the formulation and preferably 1 to 3%, by weight thereof. The total proportion of optical brightener is normally from about 0.05 to 1.5%, preferably about 0.1 to 1% and most preferably about 0.2 to 0.5%. The liquid detergent compositions according to the present invention can be manufactured by simple manufacturing methods. In a typical production method, the optical brighteners are slurried in the monohydric alcohol, after which water is added to the slurry together with a small amount of base, e.g. triethanolamine, which helps to partially dissolve the previously suspended material. Addition of the anionic detergent compound usually leads to the residual white matter being dissolved so that a clear solution is obtained. The viscosity control agent is then added -after-in-the-form-of-acid, -acid salt or completely neutralized salt, preferably as sodium or potassium salt, and stirring is continued until the solution is clear, which normally takes about 5 to 10 minutes. At this stage, the main detergent is added, i.e. the nonionic agent, together with a minor amount of acid for pH control, the pH value generally being adjusted to a value at which the proteolytic enzyme used is most stable. The solution is then stirred and the adjuvants, such as perfume and dyes are added, white liquor gives the product its final desired properties. The protease and cl-amylase enzyme preparations are then added to the solution and mixed with it as a final step in the preparation of the liquid detergent preparation. If desired, the viscosity control agent may be introduced at an earlier stage of manufacture.

The above-mentioned working steps can be carried out at room temperature, although suitable temperatures in the range 200 to 500 ° C can be used as desired, provided, however, that the temperature when adding volatile substances, e.g. perfume, should be so low that no unwanted losses occur. The product obtained has Q - ~ «-« - <- -f__w. -i,. _. A pH in the range of 7 to 10, and a density in the range of 0.9 to 1.1, preferably from 0.95 to 1.05. The viscosity of the final product at 240 DEG C. will be in the range of 60 to 150 centipoise, preferably from about 80 to 140 centipoise, and most preferably from about 115 to 135 centipoise, according to measurements performed at room temperature with a Brookfield viscometer.

The present formulations are effective and easy to use. Compared with high-performance powdered household detergents, a much "smaller" volume of the available liquids is used to obtain comparable cleaning of dirty laundry. For example, when using a typical preferred formulation according to the invention, only about 60 grams or 1/4 cup of liquid is needed for a whole batch of laundry in a top-loading automatic washing machine in which the water volume is 55 to 75 liters; and even less (about half) in a front-loading machine. The content of liquid detergent preparation in the washing water is thus of the order of 0.1%. The proportion of liquid detergent composition in the wash water is usually in the range from about 0.05 to 0.3%, preferably from 0.08 to 0.2%, and most preferably from about 0.1 to 0.15%. The proportions of the various constituents in the liquid preparation can vary to a corresponding degree. Equivalent results can be achieved by using a larger proportion of a more dilute preparation, but the larger amount required requires additional packaging volume and ¿is generally less suitable for consumer use. A A more dilute product also becomes more prone to freezing in cold weather, and is more easily exposed to hydrolysis and chemical changes during storage. 460 726 Example 1 A liquid detergent formulation (enzyme free) such as; designated "A" was prepared by mixing at room temperature the following ingredients in the proportions given: ingredient wt% ethoxylated C12-C15 primary alcohol 32.0 '(7 mol BO / mol alcohol) sodium dodecylbenzenesulfonate 7.0 triethanolamine 2.8 ethanol 5.0 '"ñ'åïší'iïb'šmíššmh"' _ 1,0 HZSO4 (conc.) 0,7 optical white flour u) 0,27 dye (2) 0,01 perfume 0,35 water residue (1) A mixture of the white goods Phorwite RKH and Phorwite BHC manufactured by Verona (2) Polar Brilhant Blue (PBB) manufactured by Ciba-Geigy.

Enzyme-containing liquid detergent preparations BU were prepared by adding different amounts of protease and d-amylase enzyme to the above-mentioned formulation A. The enzyme content in each of the detergent formulations is shown in Table 1, and is given as a percentage of enzyme formulation based on the weight of the detergent formulation. .

The protease enzyme used was a liquid enzyme preparation sold by Novo Industries, Copenhagen, 1 under the name "Alcalase" and having a concentration of 460 726 26 of 2.5 Anson units per gram of enzyme preparation. The CX amylase enzyme used was a liquid enzyme preparation sold by Novo Industries under the name "Termamyl" and has a concentration of 120,000 Novo-amylase units per gram of liquid enzyme preparation.

Test Method A total of six cotton swabs, three stained with bovine liver blood and three stained with grass, were placed 1 each in four containers in a Tergotometer vessel made by U.S. Pat. Testing Company. A series of washing tests were performed using different liquid detergent formulations, selected mixtures AU, in each container in the Tergotometer and under the following test conditions: Liquid detergent content 0.09% Stirring 100 rpm Stirring time 10 minutes Water temperature 490 C Water temperature 490 C about 150 ppm as calcium carbonate After washing, the sample patches were rinsed in tap water and then dried. The percentage of stain removal was measured by reading the values of the reflectance of each stained sample patch before and after washing, f using a Gardner XL-20 Colorimeter, and § the percentage of stain removal (% F.B) was calculated as É \ following É F a ens. = (off after washing) - (off born wash) (Rv before staining) - (Rv before washing) wherein "Rv before washing" represents the reflectance value (Rv) after staining.

The values of the percentage of stain removal calculated for each of the three sample patches having the same stain were averaged for each of the tested liquid detergent compositions. The results are shown in Table 1, which shows the percentage of F.B. for each of the tested liquid detergent formulations (formulations A to U) and the enzyme levels in these detergent formulations. 460 726 28 Table l Comparative stain removal with enzyme-containing detergent preparations Q ______ _ _ N, -., .._..._...._....._.._, .......__ prepared -% by weight%% stain removal protease (l) §L-amylase (2) blood from grass cattle liver A 0,0 0,0 42,0 31,5 B,, 50,8 37,6 C,, 52 .8 36.7 D 0.6 0.0 53.9 36.8 E 0.8 0.0 55.5 36.1 F, .44.2 37.6 G 0.2 0.2 55.3 42.4 H,, 58.4 44.8 I 0.6 0.2 60.6 44.5 J 0.8 0.2 60.5 44.1 K, 0.4 47.1 38.3 L 0.2 0.4 56.2 43.4 M,, 58.6 45.0 N 0.6 0.4 63.3 44.8 O 0.8 0.4 63.2 45.0 P,, 47.7 37.6 Q 0.2 0.6 55.4 41.3 R,, 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 0.8 47.7 36.5 jw 460 726 29 (1) The proteolytic effect of Alcalase is 2.5 Anson units per gram. A concentration of, for example, 0.2% Alcalase in the liquid detergent formulation thus corresponds to a protease enzyme activity of 0.5 Anson units (0.2 x 2.5) per 100 grams of detergent formulation. (2) The amylolytic activity of Termamyl is 120,000 Novo-amylase units per gram. A concentration of 0.2% Termamyl in the liquid detergent. the sub-preparation corresponds to a c¿-amylase enzyme activi- use On 25f999iN9y9: §mx; ꧧQh§§e§ iâfäix 120,000) per 100 grams of detergent preparation.

As shown in Table 1, the percentage stain removal (F.B) with formulation A corresponds to F.3. obtained in the absence of enzymes in the detergent composition.

Referring to F.B. data for bovine spotting blood, a comparison between the F.B. obtained with formulations F, K, P and U, all of which contain amylase enzyme but no protease enzyme and therefore are not included in the invention, that formulation P containing 0.6% by weight of OL amylase gave it the maximum achievable improvement in FB (47.7%) with amylase enzyme, i.e. an increase of about 5.7% compared to the F.B. value 42.0% for the enzyme-free preparation A. Similarly, a comparison between the F.B. obtained with formulations B, C, D and E, all of which contain protease enzyme but no amylase, that formulation E containing 0.8% protease gave the maximum enhancement (55.5%) with protease enzyme, i.e. an increase as the ring of F.B. of about 13.5% compared to the 42% F.B. is obtained with the enzyme-free preparation A. 460 726 The synergistic interaction between protease and amylase enzyme in the removal of proteinaceous spots is shown in Table 1. For example, preparation G, which contains 0.2% by weight of protease and 0.2% amylase enzyme (corresponding to an enzyme activity ratio of an amylase / protease of 24,000 Novo-amylase units per 0.5 Anson units), almost the same improvement in FB (compared to the enzyme-free formulation A) obtained with 0.8% protease in formulation E. From an economic point of view, the use of formulation G containing a mixture of enzymes according to the invention apparently means a considerably reduced need for relatively expensive protease enzyme, compared to brought with preparation E.

The highest stain removal percentage was obtained with formulation N. In particular, the combination of 0.6% by weight of protease and 0.4% by weight of amylase in formulation N gave a more than 21% increase in the FB percentage for blood stains compared to the enzyme-free preparation A. The 63.3% FB thus obtained with preparation N is considerably higher than the maximum F.B. which could be achieved with detergent preparations containing protease enzyme in the absence of eL-amylase. The enzyme activity ratio of the amylase / protease of this preparation N is 48,000 Novo-amylase units per 1.5 Anson units.

The synergistic interaction between protease enzyme and ut-amylase enzyme is also apparent from F.B. data for grass spotting. Formulation H containing 0.2% amylase enzyme and 0.4% protease enzyme gave a significantly higher F.B. than that; which can be achieved with detergent formulations containing either protease or amylase as individual enzymes in the formulation.

Claims (13)

10 15 20 25 30 460 726 3! P a t e n t k r a v An enzyme-containing liquid detergent composition, comprising: (a) from about 5% to about 75% by weight of one or more detergent surfactants selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergent compounds; (b) from about 25% to 85% by weight of water; and (C) an enzyme mixture consisting essentially of an alkaline "šïöEëâšèHš§m" b¿ñ "ë fi š" ïiïEš§ïäšënzyme in that the protease enzyme and the characterized O mixture is from about 4000 to about 80,000 Novo-amylase units of CX-amylase per Anson unit of protease, which protease is present in an amount giving from about 0.25 to about 2.5 Anson units per 100 grams of detergent composition. . Detergent composition according to claim 1, characterized in that the ratio of the enzyme activities in the enzyme mixture is from about 15,000 to 40,000 Novo-amylase units (X-amylase per Anson unit protease, which protease is present in an amount which gives from about 0.5 to about 2.0 Anson units per 100 g of detergent composition. Detergent formulation according to claim 2, characterized in that the ratio of the enzyme activities is from about 30,000 to about 40,000 Novo-amylase units of 04-amylase per Anson unit of protease. 460 726 10 15 20 25 32 Detergent formulation according to claim 1, characterized in that the cleaning surfactants consist essentially of from about 20% to about 40% by weight of a water-soluble nonionic detergent in the form of a C2-C3 alkoxylated C10-C18 alkanol and from about 4%. to 12% by weight of an anionic detergent in the form of a water-soluble salt of a C10-C15 alkylbenzene sulfonate; and which further contains from about 3 to 15% by weight of a lower alkanol selected from a lower monoalcohol having 1 to 4 carbon atoms, a lower polyol having 2 to 3 carbon atoms and mixtures thereof. Detergent composition according to claim 1, characterized in that it further contains from about 0.5% to 5% by weight of a viscosity regulating agent selected from water-soluble form salts and dibasic acids of the formula (CH2) n (COOH) 2 wherein n is 1 to 6. A detergent composition according to any one of claims 1 to 5, characterized in that it consists essentially of: (a) from about 20% to about 40% by weight of nonionic detergent compound consisting essentially of a water-soluble C2-C3 alkoxylated C10-C18 alkanol; (b) from about 4% to about 12% by weight of anionic detergent compound consisting essentially of a water-soluble salt of a C 10 -C 15 alkylbenzene sulfonate; (c) from about 3 to 15% by weight of lower alkanol selected from lower monohydric alcohols having 1 to 4 carbon atoms, lower polyols having 2 to 3 carbon atoms and mixtures thereof; 460 726 33 (d) from about 0.5 to 5% by weight of viscosity control agent consisting essentially of a water-soluble formate salt; le) from about 35% to 65% by weight of water; (f) an enzyme mixture consisting essentially of an alkaline protease enzyme and a ° * -amylase enzyme in such relative proportions that the ratio of respective enzyme activities in this mixture is from about 4,000 to about 80,000 Novo-amylase units of C * -amylase per Anson unit of protease, which protease is present in an amount which gives from about "0" 5 "to" 0125 "to" about 2Ü5 Ånson units per 100 g of detergent preparation. Detergent formulation according to claim 6, characterized in that it additionally contains from 0.1 to 5% by weight of alkanolamine. Detergent formulation according to claim 6, characterized in that the ratio of the enzyme activities in this enzyme mixture is from about 15,000 to about 40,000 Novo-amylase units of O <- amylase per Anson unit of protease. which protease is present in an amount giving from about 0.5 to about 2.0 Anson units per 100 g of detergent composition. Detergent formulation according to claim 8, characterized in that the ratio of the enzyme activities is from about 30,000 to about 40,000 Novo-amylase units of CX-amylase per Anson unit of protease. Detergent composition according to claim 6, characterized in that the nonionic detergent compound '460 726 10 15 20 25 30 34 34 is a polyethoxylated: C 12 -C 15 alkanol having from 3 to 12 ethylene oxide groups per mole; the anionic detergent is a C12 or C13 alkyl benzene sulfonate; the lower alkanol is ethanol or a mixture of ethanol and isopropanol; and the viscosity control agent is sodium formate. 11. A household washing method, characterized in that the stained and / or soiled textiles to be washed are contacted with an enzyme-containing liquid detergent composition comprising: (a "" "'from" 6mkringWS "tfII" Around "75iv. % of one or (b) (c) 12. when several surfactants selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergent compounds; from about 25 to 85% by weight of water; and an enzyme mixture consisting essentially of an alkaline protease enzyme and a CK-amylase enzyme in such relative proportions that the ratio of respective enzyme activities in this mixture is from about 4000 to about 80,000 Novo-amylase units of CK-amylase per Anson unit protease, which protease is present in an amount giving from about 0.25 to about 2.5 Anson units per 100 g of detergent composition. Process according to claim 11, characterized in that the ratio of the enzyme activities in the enzyme mixture is from about 15,000 to 40,000 Novo-amylase units of CK-amylase per Anson unit of protease, which protease is present in an amount which gives from about 726 460 '35 about 0.5 to about 2.0 Anson units per 100 grams of detergent preparation. A process according to claim 11, characterized in that the detergent composition consists essentially of: (a) from about 20 to about 40% by weight of nonionic detergent compound consisting essentially of a water-soluble C2-C3 alkoxylated C10-C18 alkanol; (b) from about 4% to about 12% by weight of anionic detergent compound consisting essentially of a water-soluble salt of a C 10 -C 15 alkylbenzene sulfonate; (c) from about 3 to 15% by weight of lower alkanol selected from lower monohydric alcohols having 1 to 4 carbon atoms, lower polyols having 2 to 3 carbon atoms and mixtures thereof; In (d) from about 0.5 to 5 weight! viscosity control agent consisting essentially of a water-soluble formate salt; (e) from about 35% to 65% by weight of water; (f) an enzyme mixture consisting essentially of an alkaline protease enzyme and an 04-amylase enzyme in such relative proportions that the ratio of respective enzyme activities in this mixture is from about 4,000 to about 80,000 Novo-amylase units of 04-amylase per Anson unit of protease, which protease is present in an amount giving from about 0.25 to about 2.5 Anson units per 100 g of detergent composition.