NL8304291A - ENZYME CONTAINING LIQUID WASHING AND PRE-WASHING PRODUCTS. - Google Patents

Description

tF 'i VO 5327

Enzyme containing liquid detergents and pre-wash detergents.

Generally speaking, the invention relates to enzyme-containing liquid detergents which are suitable for detergents and prewashes. More particularly, the invention relates to detergent compositions containing mixtures of protease and amylase enzymes in defined proportions which provide particularly effective removal of dirt and stains during washing.

The formulation of enzyme-containing liquid detergents has received much attention in the art. The desirability of incorporating enzymes into detergent compositions should primarily be attributed to the effectiveness of proteolytic and amylolytic enzymes in decomposing proteinaceous and starchy materials found on dirty tissues, thereby removing stains such as gravy stains, blood stains, chocolate stains and the like during washing is facilitated. However, enzymatic materials suitable for detergents, especially proteolytic enzymes, are relatively expensive. In general, they are indeed the most expensive ingredients in a typical commercial liquid detergent mixture, even when present in relatively minor amounts. In addition, an excess of enzymes in the detergent 20 is generally necessary. Due to the known instability of enzymes in aqueous mixtures, an excess of enzymes is generally added to the detergent to compensate for the expected reduction in enzyme activity during long-term storage. Consequently, the costs associated with the use of enzymes in liquid detergents have hitherto been a major obstacle to their wide-scale commercial application.

Mixtures of enzymes, for example proteases and amylases, containing detergent compositions have been extensively described in the prior art. For example, U.S. Pat.

3,630,930 a granular detergent containing about 0.5 to 20% enzyme carrier beads, which enzyme beads contain about 0.001 to 10% mixtures of protease and amylase enzymes in a protease to amylase weight ratio of 50: 1 to 1: 5. British Patent No. 1,240,058 to 8304291% * * # 2 discloses a granular detergent containing a mixture of protease and amylase enzymes in a protease to amylase weight ratio of 30: 1 to 3: 1, wherein the amylase content in the mixture is from 0.0003 to 3% by weight. U.S. Patent No. 3,931,034.5 issued to Inamorato et al. Discloses a granular detergent composition comprising a mixture of alkaline protease and α-amylase enzymes in an activity ratio of 100,000 to 400,000 Novo-amylase units of amylase per Anson unit protease.

Therefore, while the use of enzyme mixtures in granular detergent compositions is widely described in the patent literature, the mixtures themselves are, in most cases, described so broadly that they include, for example, mixtures in which the protease percentage can vary within 5 orders of magnitude ( British Patent No. 1,240,058) or the percentage of amylase may vary within 5 orders of magnitude (U.S. Patent No. 3,630,930), thereby reinforcing the belief that within these broad limits, the greater the amount and sense used, the more effective the resulting stain. In addition, the aforementioned patents, like US Patent No. 13,931,034, relate only to granular detergents and teach nothing about the use of enzyme mixtures in liquid detergents.

The invention provides an enzyme-containing liquid detergent containing the following ingredients: (a) about 5 to about 75% by weight of one or more detergent surfactants selected from the group consisting of anionic, nonionic , cationic, ampholytic and zwitterionic detergent compounds; (b) about 25 to 85% water, and (c) an enzyme mixture consisting essentially of an alkaline protease enzyme and an α-amylase enzyme in relative amounts such that the ratio of the enzyme activities is about 4,000 to about 80,000 Novo-amylase units α-amylase per Anson unit is protease-which protease is present in such an amount that about 0.25 to about 2.5 Anson-8304291 * 3 units per 100 g of detergent.

According to the method according to the invention, washing of stained and / or contaminated materials is performed by contacting these materials with an aqueous solution of the above described liquid detergent.

The invention is based on the finding that the amount of the alkaline protease enzyme, which is usually required to remove a proteinaceous stain, can be markedly reduced by combining with an amount of amylase enzyme according to the invention, so that a detergent is provided with an equivalent or improved stain removal capability, but at significantly reduced formulation costs. Unlike the prior art publications, which recommend mixing proteases and amylases within wide limits in the detergent compositions, the enzyme mixtures described herein are characterized by a synergistic interaction of protease and amylase, and include only those mixtures with a sharply defined ratio of activities.

. The activities of the alkaline protease and α-amylase enzymes are expressed in Anson units of protease and 20 Novo-amylase units of amylase, respectively. These units are commonly used in the art to describe the activity, under general conditions, of protease or amylase enzyme containing enzyme formulations.

In a preferred embodiment of the invention, the mixtures contain relative amounts of alkaline protease and α-amylase to provide about 10,000 to 50,000 Novo-amylase units of α-amylase per Anson unit protease, with an activity ratio of ca. 15,000 to 40,000 is more preferred and a ratio of about 30,000 to 40,000 is particularly desirable.

The amount of enzyme mixture present in the liquid detergent is of course to some extent a function of the amount of the wax mixture to be added to the wash solution. For detergents intended for use in concentrations of about 0.15% in the washing solution of an automatic household washing machine, a suitable amount of mixture provides about 0.25 to about.

2.5 Anson units of protease per 100 g of washing mixture, with a ratio of?. ~ 0 4 Z 9 1 * * t 4 is preferred from about 0.5 to 2.0 and about 1.5 Anson units / 100 g detergent is a particularly preferred protease concentration.

The activity of the alkaline protease enzyme, as noted above, is expressed in terms of Anson units.

The Anson hemoglobin method for determining the activity in Anson units is an art-known method for determining the activity of proteolytic enzymes, which method is described in the "Journal of General Physiology", vol. 22, p. 79-89 (1939), which publication by which reference forms part of this description. The modified Anson gemoglobin method can also be used to determine the proteolytic activity, which modified method is described in the article "Alkali-Resistant Enzyme for Detergents", S.R. Green, Soap and Chemical Specialties, p. 86, 88, 90, 94, and 133, May 1968, which publication is incorporated herein by this reference. In principle, the method uses the alkaline protease enzyme to degrade a denatured hemoglobin substrate under standard conditions in a buffered aqueous medium at the selected pH, and the amount of degraded material is determined by a color test with phenol reagent.

The activity of the α-amylase enzyme is, as previously noted, determined in terms of Novo amylase units. The standard requirement for the determination of these Novo units is a modified form of the SKB method (Sandstedt, Knee & Blish, Cereal Chemistry 16, 712, (1939)) without addition of β-amylase. According to this protocol, 20 ml of a buffered starch solution (prepared by the method described below) is metered into a test tube (diameter 24 mm, length 190 mm) and placed in a water bath at a constant temperature of 37 ° C. After preheating for a few minutes, 10 ml of the amylase solution (or v ml of amylase solution + (10-v) ml of water) to be tested is added. The contents of the tube are thoroughly mixed and a chronometer is started at the same time. At suitable intervals, 1 ml of the reaction mixture is added to 5 ml of a dilute iodine solution (prepared by the method described below), shaken and transferred to a comparison tube, and the color is compared to the standard color. When the color endpoint is reached in less than 10 minutes, a more dilute amylase solution or a * 5 τ η Λ 9 A 1 "-y" * + * 5 smaller volume of amylase solution is used.

As the colorimeter, the Sacred Comparator 607 is used with the glass-α-amylase standard (cf. Redfem, Methods for determination of α-amylase, Cereal Chemistry 24, 259, (1947)). The α-amylase activity of the sample can be calculated using the following formula:

1430 XV

A -, where

t x a x v J

A = α-amylase activity in Novo-amylase units per gram t = time to reach the color end point (minutes) a = weight of the sample in grams 10 V - volume to which the sample has been diluted (ml) v = volume of the amylase solution used (ml)

Strictly speaking, the factor "1430" is not constant, but it is to some extent a function of the quality of the starch used. For accurate determinations, the value of the factor must be calculated using a commercially available standard amylase preparation with known activity.

The above "dilute iodine solution" is prepared by dissolving 1 ml of standard iodine solution and 20 g of potassium iodide in enough water to obtain 500 ml; the standard iodine solution 20 is prepared by dissolving 11 g of iodine crystals and 22 g of potassium iodide in enough water to obtain 500 ml. The above "buffered starch solution" is prepared as follows: 10 g of soluble starch (e.g., Merck, Amylum solubile, Soluble Starch, Erg. B.6) calculated as dry matter, is made into a dispersion with a little water. The dispersion is added to about 200 ml of boiling water. When the starch is completely dissolved, the solution is cooled, transferred to a 1 L volumetric flask and made up to the mark with water. The starch solution is prepared by dissolving 9.36 g NaCl, 69.00 g KH 2 PO 4, 4.80 g Na 2 HPO 2 .2 ^ 0 in enough water to obtain 1 L. Finally, the solution is saturated with toluene. The pH of the finished buffered starch solution should be 5.7. The starch solution should be prepared as fresh as possible, but cannot be stored in a refrigerator for more than 24 hours for a period of time. Distilled water is used in all cases.

35 The enzyme activity of proteolytic and amylolytic Λ T Λ 'o Λ Ί ·. t 6 enzyme preparations are, in practice, usually determined without following the above assay instructions. Most of the commercially available liquid enzyme preparations containing protease or amylase enzymes have enzyme activity given by the manufacturer and expressed in Anson units or Novo-amylase units (or in proportional units). Optionally, the activity of a given enzyme preparation can be easily determined analytically by the method, whereby the reactivity of the enzyme with a protein or starch substrate can be determined, according to standard conditions, and then compared with the reactivity of reference enzyme preparations with a known activity. In this analytical method, the enzyme reactivity can be conveniently expressed as the optical density of a test solution containing the enzyme preparation and the protein or starch substrate when measured under standard conditions, the higher the optical density, the stronger the activity.

The suitable alkaline proteolytic enzymes include the various commercially available liquid enzyme preparations which are adapted for use in detergent compositions, powdered enzyme preparations also being useful, although as a general rule they are less suitable for incorporation into the liquid washing mixtures according to the invention. Thus, suitable liquid enzyme preparations include "Alcalase" and "Esperase" sold by Novo Industries, Copenhagen, Denmark and "Maxatase" and "AZ-Protease" sold by Gist-Brocades, Delft. "Alcalase" is particularly preferred for the detergent compositions according to the invention.

Among the suitable liquid α-amylase enzyme preparations are those marketed by Novo Industries and Gist-Brocades under the trademarks "Termamyl" and "Maxamyl", respectively. An organic solvent is preferably used in combination with water to serve as the solvent for the liquid detergent. The preferred organic solvent is a lower alkanol of 1 to 4 carbon atoms with 1 to 3, preferably 1 or 2, hydroxyl groups. The lower alkanol is more particularly ethanol or a mixture of ethanol and isopropanol, although lower monoalcohols such as propanol and butanol, and lower polyols having 2 to 3 carbon atoms tq 7 Η ζ 9 g 1 * - * 7 such as ethylene glycol and propylene glycol are useful although they are less preferred. The use of primary, secondary and tertiary butanol or of n-propanol as the lower alkanol is generally limited to mixtures thereof with ethanol, the ethanol preferably being at least 80 to 90% of these mixtures. The use of ethanol as the sole alkanol and the sole organic solvent is highly preferred. In mixtures of ethanol and isopropanol, the ethanol is preferably the major component, usually in a relative amount of 60 to 90% of the mixture, preferably about 75% {d.i. in a ratio of 3: 1). Of course, other mixtures of the different alkanols can be used, such as ethanol and propylene glycol, and in these mixtures ethanol is preferably also the main component.

The detergents according to the invention contain one or more surfactants selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergent compounds. The synthetic organic detergents used in the practice of the invention may include any of a wide variety of such compounds, which are known and described in detail in Surface Active Agents, Vol. II, 20 Schwartz, Perry and Berch, published 1958 by Interscience Publishers, the relevant parts of which are incorporated herein by reference.

The nonionic detergents are usually poly (lower alkoxylated) lipophiles, in which the desired hydrophilic-lipophilic equilibrium is obtained by adding a hydrophilic poly (lower alkoxy group) to a lipophilic moiety. For the detergent compositions of the invention, the preferred detergent is preferably a poly (lower alkoxylated) higher alkanol, the alkanol containing 10 to 18 carbon atoms and the number of moles of lower alkylene oxide (having 2 or 3 carbon atoms) being 3 to 12 . These materials preferably use those in which the higher alkanol is a higher fatty alcohol of 11 or 12 to 15 carbon atoms and which contains 5 to 8 or 5 to 9 lower alkoxy groups per mole. Preferably the lower alkoxy is ethcocyte, in some cases it may be desirable to be mixed with propoxy, the latter, if present, usually being a minor component (less than 50%). Examples of such compounds 3 3) -: - 251 * * · 8 are those in which the alkanol contains 12 to 15 carbon atoms and which approx.

E) contains 7 ethyl groups per mole, for example, Neodox ^ 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 having an average of 12 to 15 carbon atoms, with about 7 moles of ethylene oxide, and the latter is a corresponding mixture in which the carbon atoms content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups per mole averages about 6.5. The higher alcohols are primary alkanols. Other examples of such detergents include Tergitol 15-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 an 11-15 carbon atoms per molecule containing linear secondary alkanol with 7 moles of ethylene oxide, and the latter is a similar product, however, obtained by conversion of 9 moles of ethylene oxide.

Also useful in the detergent compositions of the invention are higher molecular weight nonionic detergents such as Neodol 45-11 which are similar condensation products of ethylene oxide and higher fatty alcohols, the higher fatty alcohols containing 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 detergents are, for example, Plurafac B-26 (BASF Chemical Company), the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxide.

Preferred poly (lower alkoxylated) higher alkanols provide the best equilibrium between hydrophilic and lipophilic units when the number of lower alkoxy groups is about 40 to 100% of the number of carbon atoms in the higher alcohol, preferably 40 to 60% of that. The nonionic detergent preferably consists of at least 50% of preferred ethoxylated alkanols. Higher molecular weight alcohols and various other normally solid nonionic detergent compounds and surfactants may contribute to gelatinization of the liquid detergent composition and consequently they are usually omitted from the detergent compositions of the invention or their amount limited therein, although minor relative amounts thereof may be used because of their cleaning properties, etc. In both preferred and less preferred nonionic detergents, the alkyl groups contained therein are preferably linear, although to a lesser extent, minor branching may be accepted, such as with a carbon adjacent to or two carbon atoms from the straight chain terminal carbon and from the ethoxy chain side, provided that this alkyl branch contains no more than three carbon atoms. Normally, the carbon atom content in such a branched configuration is small, rarely more than 20% of the total carbon atom content in the alkyl. Likewise, while linear alkyl groups terminally linked to the ethylene oxide chains are highly preferred and believed to result in the optimal combination of cleaning performance, biodegradability and non-gelatinizing properties, a medial or secondary bond to the ethylene oxide occur in the chain. In these cases, this usually takes place only in minor proportions of these alkyls, generally less than 20%, but as in the case of the aforementioned Tergitols, it may be greater. Also, when propylene oxide is present in the lower alkylene oxide chain, this relative amount is usually less than 20% and preferably less than 10% thereof.

In addition to the nonionic detergent, which is the major synthetic organic detergent in the detergent compositions of the invention, an anionic detergent can be used. The most preferred anionic detergent compounds are the higher (10 to 18 or 20 carbon atoms) alkyl benzene sulfonate salts, wherein the alkyl group preferably contains 10 to 15 carbon atoms, and more particularly is a straight chain alkyl radical having 12 or 13 carbon atoms. Preferably, such an alkyl benzene sulfonate has a high content of 3- (or higher) phenyl isomers and a correspondingly low (usually much less than 50%) content of 2- (or lower) phenyl isomers; in other words, the benzene ring is preferably largely bound to the 3-, 4-, 5-, 6- or 7-positions of the alkyl group and the content of isomers in which the benzene ring is bound to the 1 or 2- 10 place is correspondingly small. Typical alkylbenzene sulfonates surfactants are described in U.S. Patent No. 3,320,174. Of course, more branched alkyl benzene sulfonates can also be used, but usually they are not preferred due to the fact that they are not biodegradable.

5

Other useful anionic detergents are the olefin sulfonate salts. Typically, these contain long chain alkenyl sulfonates or hydroxyalkane sulfonates (where the OH is bonded to the carbon atom which is not directly bonded to the -SO 2 H group-bearing carbon atom) long chain. The olefin sulfonate detergent usually consists of a mixture of these types of compounds in varying amounts, often together with disulfonates or long chain sulfate sulfonates. Such olefin sulfonates are described in many patents, such as in 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. The number of carbon atoms in the olefin sulfonate is usually between 10 and 25, more often 10 to 18 or 20, for example a mixture mainly of and C c, with an average of about 14 carbon atoms, or a mixture of 1 ° mainly of C ^, and C ^ g, with an average of about 16 carbon atoms.

Another class of useful anionic detergents is that of the higher paraffin sulfonates. These may preferably be primary paraffin sulfonates, which are prepared by reacting long chain alpha olefins and bisulfites, e.g. sodium bisulfite, or paraffin sulfonates with sulfonate groups distributed along the paraffin chain, such as the products obtained by reacting a long wax paraffin chain with sulfur dioxide and oxygen under ultraviolet radiation, followed by neutralization with sodium hydroxide or another suitable base (such as, for example, in U.S. Patent Nos. 2,503,280; 2,507,088; 3,260,741; 3,372,188; and German Patent 735,096 ). The paraffin sulfonates preferably contain 13 to 17 carbon atoms and they normally consist of the monosulfate, but if desired they can be di-, tri- or higher sulfonates. The di- and polysulfonates are typically used as mixtures with a corresponding monosulfonate, for example as an approx. 30% disulfo

• $ X 0 A 0 f! I

The mixture of mono- and disulphonates containing a carbonate substituent is preferably linear / but if desired branched chain paraffin sulphonates may be used, although they are not as good in biodegradability .

Other suitable anionic detergents are sulfated. ethoxylated higher fatty alcohols of the formula RO (H ^ O) ^ SO, wherein R is a fatty alkyl group having 10 to 1.8 or 20 carbon atoms, m equals 2 to 6 or 8 (preferably with a value of 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 alkyl benzene sulfonate, wherein the higher alkyl group contains 10 to 15 carbon atoms . As is the case with the preferred nonionic detergent, the alkyl in the anionic alkoxylate detergent preferably consists of a mixture of 15 different chain lengths, for example chains with 11, 12, 13, 14 and 15 carbon atoms or chains with 12 and 13 carbon atoms, rather than from chains all the same length.

Ethylene oxide is the preferred lower alkylene oxide of the anionic alkoxylate detergent, as it is in the nonionic detergent, and the relative amount thereof in the polyethoxylated higher alkanol sulfate is preferably 2 to 5 moles of ethylene oxide groups per moles of anionic detergent, with 3 moles being most preferred, especially when the higher alkanol contains 11 or 12 to 15 carbon atoms. To maintain the desired hydrophilic-lipophilic balance, when the carbon atom content of the alkyl chain is in the lower portion of the range of 10 to 18 carbon atoms, the ethylene oxide content of the detergent can be reduced to about 2 moles per mole, while number of ethylene oxide groups, when the higher alkanol contains 16 to 18 carbon atoms, i.e. in the higher part of the region, are increased to 4 or 5 and in some cases even to 8 or 9. Similarly, the salt-forming cation can be chosen, that the best solubility is obtained. It can be any suitably solubilizing metal or radical, but most often it is alkali metal, for example sodium, or ammonium. When lower alkylamino or alkanolamine groups are used, the alkyl groups and alkanols usually contain 1 to 4 carbon atoms * T ~ f) Λ -f

“M

11% «12 and the amines and alkanolamines can be monosubstituted, twofold or tripled, as is the case with monoethanolamine, diisopropanolamine and trimethylamine.

The poly (lower alkoxy) higher alkanol sulfates can be used in place of or in combination with other preferred anionic detergents, such as the higher alkyl benzene sulfonates, to supplement the nonionic detergent in the detergent compositions of the invention. A preferred polyethoxylated alcohol sulfate detergent can be obtained from Shell Chemical Company and is marketed as Neodol 25-3S.

Examples of higher alcohol polyethenoxy sulfates which can be used in the detergent compositions of the present invention include: mixed carbon monoxide. or primary alkyl triethylenoxysulfate, as the sodium salt; myristyl triethenoxy sulfate, as the potassium salt; n-decyl dietheno-15 xysulfate, as diethanolamine salt; lauryl diethenoxysulfate, as ammonium salt; palmityl tetraethylene sulfate, as sodium salt; mixed normal primary alkyl, mixed tri and tetraethenoxy sulfate, as sodium salt; as stearyl pentaethyl oxysulfate, as trimethylamine salt, and mixed C 1-4 normal primary alkyl triethenoxy sulfate, as potassium salt.

Other useful anionic detergents include the higher acyl sarcosinates, eg sodium N-lauroyl sarcosinate; higher fatty alcohol sulfates, such as sodium lauryl sulfate and sodium talc alcohol sulfate; sulfated oils; sulfates of mono- or diglycerides of higher fatty acids, for example stearine monoglyceride monosulfate, although the sodium-higher alcohol sulfates were found to be less good than the polyethoxylated sulfates in terms of washing power; aromatic poly (lower alkenoxy) ether sulfates, such as the sulfates of the condensation products of ethylene oxide and nonyl phenol (usually 1 to 20, preferably 2 to 12, oxyethylene groups per molecule), polyethoxy-30 higher alcohol sulfates, and alkyl phenol polyethoxy sulfates having lower alkoxy substituent (having 1 to 4 carbon atoms, e.g. methoxy) to a carbon where it is the sulfate-bearing carbon atom, such as monomethyl ether monosulfate of a long chain vicinal glycol, for example a mixture of vicinal alkane diols having 16 to 20 carbon atoms in a straight chain; acyl esters of isethionic acid, for example oleyl isethionates; acyl-N-methyltaurides, for example potassium-N-methyl-83 ··; 42 91 13 lauroyl or oleyl taurides? higher alkylphenyl polyethoxysulfonates; higher alkyl phenyl disulfonates, for example pentadecyl phenyl disulfonate; and soaps of higher fatty acids, for example, soaps from mixed coconut oil and tallow oil in a ratio of 1: 3.

Of the aforementioned types of anionic detergents, the sulfates and sulfonates are generally preferred, but the corresponding phosphates and phosphonates can also be used if their phosphorus content is not objectionable. Generally, the water-soluble anionic synthetic organic detergents (including soap), as previously indicated, are salts of alkali metal cations, such as of potassium, lithium and especially sodium, although salts of ammonium and substituted ammonium cations, such as those previously described, triethanolamine, triisopropylamine, can also be used. With regard to the aforementioned examples of water-soluble anionic detergents, the sodium, potassium, ammonium and alkanol ammonium salts should be considered to be individually listed for each detergent.

Ampholytic detergents can be used in the detergent compositions of the invention in minor amounts to replace the anionic detergents or a portion thereof or to replace a portion of the nonionic detergent. Ampholytic detergents include the higher fatty carboxylates, phosphates, sulfates, or sulfonates, which contain a cationic substituent, such as an amino group, which may be quaternized, for example, with a lower alkyl group, or whose chain may be extended the amino group by condensation with a lower alkylene oxide, for example ethylene oxide.

Generally, these detergents containing ampholytic or cationic detergents will not be as effective and may have a greater tendency to gel or thicken upon standing. Therefore, they are often avoided. However, if these properties are not objectionable, use can be made of minor relative amounts of ampholytic products, such as Miranol C2M, sold by Miranol Chemical Company, or Deriphat 151, a sodium N-coconut betamine propionate, in the marketed by General Mills, 35 Ine. A cationic detergent, which may be useful at times, is distearyl dimethylammonium chloride (which has a fabric softening effect) and the 3 - n /, 9 0 1 v '* y,']. 14 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, to prevent gelatinization at low temperatures and to allow a reduction in the lower alkanol solvent content is preferably a water-soluble formate. Sodium formate is preferred, but alkali metal formates can be used, for example, potassium formate and various other water-soluble formates, including formic acid, which can be added to the liquid detergent in which it dissolves, ionizes and / or reacts to form substantially the same type of liquid detergent resulting from the addition of the alkali metal formate in salt form. Other useful formates are those of water-soluble cations, as previously described as salt-forming cations for anionic detergents. although formate is the preferred viscosity control agent, it has been found that various salts of two basic acids can also be used successfully, including disodium adipate, referred to herein as sodium adipate, being the best. Other salts of dibasic acids of the formula (CH, J (COOH) -, zn z 20 where n equals 1 to 6) can also be used and in some cases the salts of monounsaturated acids with the same chain length and configuration Highly preferred, however, is the use of the straight chain saturated aliphatic terminally carboxylated compounds It is more preferred to use those where n equals 3 to 5, more particularly 4, and wherein the acid is completely neutralized, although, however, the acidic salts can also be used.

Among the dibasic acids which can be used, either as the mono or di salts, are malonic, succinic, glutaric, adipic, and pimelic. An unsaturated divalent acid, maleic acid, can also be used, at least in part.

The acids can be used without prior neutralization, or they can be used in the form of salts, such as disodium malonate, monopotassium succinate, di-trianolamine glutarate, disodium adipate and monosodium pimelate.

In order to contribute to the solubilization of the 3 3 0 Λ 2 9 1 * * 15 detergents and the optical brighteners optionally present in the liquid detergents of the invention, a small relative amount of alkaline material or a mixture of such materials is often included in the recipes according to the invention. Suitable alkaline materials include mono-, di- and trialkanolamines, alkylamines, ammonium hydroxides. Of these materials, the alkanolamines, preferably the trialkanolamines, and more particularly triethanolamine, are preferred. The pH of the finished liquid detergent containing such basic material is usually neutral or weakly basic. Satisfactory pH ranges are from 7 to 10, preferably from about 7.5 to 9, and more particularly from about 7.5 to 8.5.

The optical fluorescent bleaches or whiteners used in the liquid detergents are important components of modern detergents which give the wax and materials a clear appearance, in that the wax is not only clean but also looks clean.

Although it is possible to use a single whitener for a special purpose in the liquid detergent of the invention, it is generally desirable to use blends of whiteners, all of which have a good whitening effect on cotton, nylon, polyester, and mixtures of these materials which are also resistant to bleaching. A good description of these types of optical brighteners can be found in the article "The Requirements of Present Day Detergent Fluorescent Whitening Agents" by A.E. Siegrist, J. Am. Oil Chemists Soc., January 1978 (Volume 55). This article and U.S. Patent No. 3,812,041, issued May 21, 1974, both of which are incorporated by this reference as appropriate herein, contain detailed descriptions of a wide variety of suitable optical brighteners.

Among the whiteners useful in the liquid detergents of the invention are: Calcofluor 5BM (American Cyanamid); Calcofluor White ALF (American Cyanamid); SOF A-2001 (Ciba); CDW (Hilton-Davis); Phorwite RKH, Phorwite BBH and Phorwite BHC (Verona); CSL, powder, acid (American Cyanamid); FB 766 (Verona); Blancophor PD (GAF); UNPA (Geigy); Tinopal RBS 200 (Geigy). The acidic or "nonionic" forms of the brighteners tend to become soluble by the alcohols of the formulations of the invention, while the salts tend to dissolve in water.

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v r. V J

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16

Adjuvants can be present in the liquid detergents to impart additional properties, either functional or aesthetic. Among the useful adjuvants are agents to suspend or prevent redeposition thereof, such as polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxypropylmethyl cellulose; thickeners, for example resins, alginates, agar agar; foam improvers, for example laurine myristine diethanol amide; anti-foaming agents, for example silicone; bactericides, e.g. tribromosalicylanilide, hexachlorophene; dyes, pigments (dispersible in water 1.0), preservatives, ultraviolet absorbers, fabric softeners, opacifiers, for example polystyrene suspensions, and perfumes. Obviously, such materials are selected on the basis of the properties desired in the finished product and so that they are compatible with the other ingredients thereof. Other adjuvants that may be used are divalent or trivalent lower alcohols which, in addition to being solvents and lowering the flash point of the product, may act as antifreeze components and improve the compatibility of the solvent system with certain product components . Of these compounds, the most preferred group includes the lower polyols having 2 to 3 carbon atoms, for example ethylene glycol, propylene glycol and glycerol, but the lower alkyl (CC) ether derivatives of these compounds, known under 14 as Cellosolve, may also be used. The relative amounts of these lower alkanol substitutes are normally limited to more than 20% of the total alcohol content of the liquid detergent.

Another category of useful additives are hydrotropics which serve to improve the aqueous solubility of components that otherwise have limited water solubility. Useful hydrotropes include the alkali metal, ammonium, and ethanolamine salts of the following acids: (1) aryl sulfonic acids, such as benzene sulfonic acid, and C 1 -C 2 alkyl substituted benzene sulfonic acids, for example, toluene sulfonic acid and xylene sulfonic acid; and (2) C -C-alkyl-sulfur-

D O

acids, such as hexyl sulfuric acid.

The relative proportions of the various components of the liquid detergent compositions according to the invention are important. 2 9 1 17 for the production of a uniform product with a desirable viscosity and an acceptable action as a total detergent, which does not gel at low temperatures or in an open package at room temperature.

In order to promote the solubility of the fluorescent whiteners and other ingredients in the detergent composition and to prepare a clear, homogeneous and easily pourable product, 10 to 60% of the total liquid detergent concentrate should be nonionic detergent. Preferably, the nonionic detergent content, especially when an anionic detergent is present in the liquid product, is 2 to 40% and more particularly 3 to 40%, while the best known recipe at present Contains 32%.

The anionic detergent content is usually in the range of 3 to 15%, preferably 4 to 12% and more particularly 6 to 10%, the best known recipe at this time containing about 7% thereof. The ratio of total nonionic detergent to anionic detergent is normally 15: 1 to 1: 1, 8: 1 to 2: 1, and preferably 5: 1 to 3: 1.

The lower alkanol is generally present in the liquid detergents in an amount sufficient to aid the dissolution and / or stabilization of the various ingredients in the final product. The contents of the lower alkanol used are normally about 3 to 15%, preferably 4 to 12%, more preferably 4 to 8%, and most preferably about 5% at this time.

The content of used agent for controlling the viscosity or a mixture of such agents is normally 0.5 to 5%, based on the finished liquid detergent, preferably about 0.5 to 3% and preferably about 1% .

The water content, the major solvent in the detergent compositions of the invention, is usually about 25 to 85%, preferably 35 to 65%, and more preferably about 40 to 55% (wt%) of the liquid detergent . The most preferred recipes contain about 45 to 50% water.

The alkaline additive content, such as triethanol-35 amine, in the liquid detergent is usually about 0.1 to 5% by weight, and preferably 1 to 3% by weight, based on the detergent. The total content of 3 T 9 Λ 9 Λ 1 ·> V, V ΰ 'i J i ----—' · 18 optical whitener stop is usually about 0.05 to 1.5%, preferably about. 0.1 to 1% and more particularly about 0.2 to 0.5%.

The liquid detergents of the invention can be prepared by simple manufacturing techniques. According to a typical manufacturing method, the optical brighteners are dispersed in the monovalent alcohol, then water is added to the dispersion along with a small amount of a base, such as triethanolamine, which helps to partially dissolve the previously suspended material. Addition of the anionic detergent compound usually results in the rest of the whitener dissolving to form a clear solution. The viscosity control agent is then added in the form of the acid, the acidic salt or completely neutralized salt, preferably as the sodium or potassium salt, and stirring is continued until the solution becomes clear; which normally takes about 5 to 10 minutes. At this time, the major detergent, the nonionic detergent, is added along with a minor amount of acid to control the pH, which is usually adjusted to a value at which the proteolytic enzyme used is the most stable. This is followed by stirring the solution and adding adjuvants, such as perfume and colorant, which gives the product its final desired properties. The protease and α-amylase enzyme preparations are then added to the solution and mixed as the final step of the preparation of the product, namely the liquid detergent. If desired, the viscosity control additive can be added at an earlier processing stage.

The above operations can be carried out at room temperature, although suitable temperatures of 20 to 50 ° C can be used, if desired, with the proviso that when volatile materials such as perfume are added, the temperature should be sufficiently low to avoid objectionable losses.

The product obtained usually has a pH of between 7 and 10, and a density of from 0.9 to 1.1, in particular from 0.95 to 4.15, D5: The viscosity of snab ££ peiadproduct at 24? The range is from 60 to 150 cP, in particular from about 80 to 140 cP, and more particularly from about

115 to 135 cP, according to measurements made with a Brookfield viscometer at room temperature.

8304291

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19

The liquid detergents according to the invention are effective and easy to use. Compared to powdered total detergents, much smaller volumes of the fluids of the invention are used to achieve comparable cleaning of dirty laundry. For example, when using a typical preferred product of the invention, only about 60 g of liquid is required for a full wash tub in an automatic top loading washing machine, in which the water volume is 55 to 75 L, and even less, about half. required for front loading machines. Thus, the concentration of the liquid detergent in the wash water is of the order of about 0.1%. Usually, the liquid detergent content in the wash solution is about 0.05 to 0.3%, preferably 0.08 or 0.2%, and more particularly about 0.1 to 0.15%.

The contents of the various components of the liquid detergent 15 can vary accordingly. Similar results can be obtained by using larger relative amounts of a more dilute product, but the required larger amount requires additional packaging and is generally less suitable for the user. Also, more dilute products have a stronger tendency to freeze in cold weather, and they can be stronger

subject to hydrolysis and chemical changes upon storage. example I

A liquid detergent (containing no enzymes), designated as detergent "A", was prepared at room temperature by mixing the following ingredients in the indicated relative amounts:

Ingredient Wt% ethoxylated primary C 2 - C 15 ~ 32.0 alcohol (7 moles EO / mole alcohol) sodium dodecylbenzenesulfonate 7.0 30 triethanolamine 2.8 ethanol 5.0 sodium formate 1.0 H 2 SO. (concentrated) 0.7 ^ 4 (1) optical brighteners 0.2735 dye ^ 0.01 perfume 0.35 water residue 8304291. _._. tl 20

Footnote to Table (1) a mixture of the whiteners Phorwite RKH and Phorwite BHC, which are manufactured by Verona.

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

The enzyme-containing liquid detergents BU were formulated by adding varying amounts of protease and α-amylase enzymes to the above detergent A. The enzyme concentration in each of the detergents is shown in Table 1, expressed as percent enzyme preparation, by weight of the detergent. The protease enzyme used was a liquid enzyme preparation, which is marketed under the trademark "Alcalase" 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 which is marketed under the trade name "Termamyl" by Novo Industries at a concentration of 120,000 Novo amylase units per gram of liquid enzyme preparation.

Test prescription

A total of six cotton rags, three with bovine liver blood stains and three with grass stains, were placed in each of four buckets of 20 by one. Testing Company manufactured Tergotometer barrel placed.

A series of washing tests were carried out using a different liquid detergent selected from the detergents A.ü in each bucket of the Tergotometer under the following test conditions: concentration of the liquid detergent 0.09% stirring speed 100 rpm duration of stirring for 10 minutes

water temperature 48.9 ° C

water hardness approx. 150 ppm as calcium carbonate. At the end of the washing treatment, the samples were rinsed in tap water and then dried. The stain removal rate was measured by reflectance measurements on each stain test patch prior to and after the wash using a Gardner XL-20 Colorimeter, and the soil removal rate (VV%) was calculated as follows: $ ”Λ- /,» ') Λ j

& V 'J · - / ": / I

21 v v - (BA after washing) - CRD before washing) - (Rd before staining) - (Rd before washing) where "Rd before washing" is the Rd value after staining, or soiling.

The soil removal rate values calculated for each of the three test stains with the same stain were averaged for each liquid detergent tested. The results are shown in Table 1 which lists the soil removal rate for each of the liquid detergents tested (detergents A-ü) and the enzyme concentration of these detergents.

TABLE 1

Comparative stain removal with enzyme-containing detergents

Detergent Protease ^ a-Amylase ^ Stain removal,% wt% wt% Bovine liver Grass _ _ _ blood _ A 0.0 0.0 42.0 31.5 15 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 20 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 25 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 0 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 30 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 0.8 47.7 36.5 (1) The proteolytic activity of Alvalase is 2.5 Anson units per 35 grams. Thus, a concentration of, for example, 0.2% Alcase in the liquid detergent corresponds to a protease enzyme activity of 0.5 Anson units (0.2 x 2.5) per 100 g of detergent.

(2) The amylolytic activity of Termamyl is 120,000 Novo amylase units per gram. Thus, a concentration of 0.2% Terma-40 myl in the liquid detergent corresponds to α-amylase enzyme activity of 5 ^ -}--V 7 7 7 7 7 7 7 7 7 7 7 7 __ __ __ __ __ __ __ __ __ __ __ __ __ __. 4 22 24,000 Novo-amylase units (0.2 x 120,000) per 100 g of detergent.

As indicated in Table 1, the percentage of stain removal (V.V.) achieved with detergent A is V.V. achieved in the absence of enzymes from the detergent. Regarding the 5 VV data for the bovine liver blood stain, comparing the detergents F, K, P and U containing all amylase enzyme but no protease and therefore not according to the invention shows that the VV 0.6 wt.% Α-amylase-containing detergent P the maximum improvement of the VV with amylase enzyme (47.7%) op-10 verde, which is an improvement of about 5.7% compared to the VV value of 42.0% for the enzyme-free detergent A. Similarly, when comparing the the detergents B, C, D and E, which contain all protease enzyme but no amylase, VV, that the 0.8% protease containing detergent E achieved the maximum improvement of the VV (55.5%) with protease enzyme, i.e. an increase of about 13.5% over the V.V. achieved with the enzyme-free detergent A. of 42%.

The synergistic interaction of the protease and amylase enzymes to remove proteinaceous surfaces is shown in Table 1. For example, detergent G containing 0.2 wt% protease-20 enzyme and 0.2 wt% amylase enzyme (corresponding to an activity ratio of amylase enzyme and protease enzyme of 24,000 Novo-amylase units per 0.5 Anson units) almost the same improvement in VV to (relative to the enzyme-free detergent A) when achieved with 0.8 wt% protease in detergent E. Economically, the use of detergent G, which contains a mixture of enzymes according to the invention, means a marked reduction in the need for the relatively expensive protease enzyme, compared to detergent E.

The highest dirt removal rate was achieved with detergent N. Specifically, the combination of 0.6 wt% protease 30 and 0.4 wt% amylase in detergent N provided an improvement of more than 21% in the soil stain removal rate over the blood stain. enzyme-free detergent A. Thus, the VV achieved with detergent N is of 62.3% considerably larger than the maximum V.V. which could be obtained with protease enzyme in the absence of α-amylase-containing detergents. The activity ratio of amylase enzyme and protease enzyme of this detergent N is 48,000 Novo amylase units per 1.5 Anson units.

8 J π λ o ts 1 23

The synergistic action of protease enzyme and α-amylase enzyme is also evident from the grass stain VV data. For example, detergent E containing 0.2% amylase and 0.4% protease provided a significantly stronger V.V. that could be achieved with either protease or amylase as individual enzyme containing detergents.

Π Ί - i η 0 1

Claims (13)

Enzyme-containing liquid detergent, characterized in that it contains the following ingredients: (a) about 5 to about 75% by weight of one or more detergent surfactants selected from the group consisting of 5 anionic, nonionic, cationic, ampholytic and zwitterionic detergent compounds; (b) about 25 to 85% water, and (c) an enzyme mixture consisting essentially of an alkaline protease enzyme and an α-amylase enzyme in such relative amounts that the ratio of the enzyme activities is about. 4,000 to about 80,000 Novo-amylase units is α-amylase per Anson unit protease, which protease is present in such an amount that about 0.25 to about 2.5 Anson units per 100 g detergent. Detergent according to claim 1, characterized in that the ratio of the enzyme activities in the enzyme mixture is about 15,000 to about 40,000 Novo-amylase units ct-amylase per Anson unit protease 20 and this protease is present in an amount to provide from about 0.5 to about 2.0 Anson units per 100 g of detergent. Detergent according to claim 2, characterized in that the ratio of the enzyme activities is about 30,000 to about 40,000 Novo-amylase units α-amylase per Anson unit protease. Detergent according to claim 1, characterized in that the surface-active detergents consist essentially of about 20 to about 40% by weight of a water-soluble C 1 -C 20 alkoxylated C 1 -C 20 alkanol as non ionic detergent and about 4 to 12% by weight of a water-soluble salt of a C 1 -C 6 -alkylbenzenesulfonate as anionic detergent? 30 additionally containing: about 3 to 15% by weight of a lower alkanol selected from the group consisting of a lower monoalcohol with 1 to 4 carbon atoms, a lower polyol with 2 to 3 carbon atoms and mixtures thereof. 9304291 Detergent according to claim 1, characterized in that it additionally contains about 0.5 to 5% by weight of a viscosity control agent selected from the group consisting of water-soluble formate salts and dibasic acids with the formula 5 (CH2) n (CQOH) 2, wherein n is 1 to 6. Enzyme-containing liquid detergent, characterized in that it consists essentially of (a) from about 20 to about 40% by weight of a nonionic detergent compound consisting essentially of a water-soluble C2- C 2 -alkoxylated C 1 -C 18 alkanol, (b) about 4 to about 12% by weight of an anionic detergent compound consisting essentially of a water-soluble salt of a C 1 -C 2 alkylbenzenesulfonate, (c) about 3 to 15% by weight of a lower alkanol selected from the group consisting of a lower amimo alcohol of 1 to 4 carbon atoms, a lower polyol of 2 to 3 carbon atoms and mixtures thereof, 20 (d) about 0, 5 to 5% by weight of a viscosity control agent consisting essentially of a water-soluble formate salt, (e) about 35 to 65% by weight of water, and (f) an enzyme mixture consisting essentially of a alkaline protease enzyme and an α-amylase enzyme in such relative amounts that the ratio of the respective enzyme activity in the mixture, it is from about 4,000 to about 80,000 Novo-amylase units of α-amylase per Anson unit protease, the protease being present in an amount such that about 0.25 to about 2 .5 Anson units per 100 g of detergent are provided. Detergent according to claim 6, characterized in that it additionally contains 0.1 to 5% by weight of an alkanolamine. Detergent according to claim 6, characterized in that the ratio of the enzyme activities in the enzyme mixture is about 15,000 to about 830-12 fl1 40,000 Novo-amylase units α-amylase per Anson unit protease and that the protease is present in an amount to provide from about 0.5 to about 2.0 Anson units per 100 g of detergent. Detergent according to claim 8, characterized in that the ratio of the enzyme activities is about 30,000 to about 40,000 Novo-amylase units α-amylase per Anson unit protease. 10. Detergent according to claim 6, characterized in that the non-ionic detergent compound is a polyethoxylated -C 1 -alkanol with 3 to 12 ethylene oxide groups per mole, that the anionic detergent is a C 1 or 4 alkylbenzenesulfonate, that the lower alkanol is ethanol or a mixture of ethanol and isopropanol and that the viscosity control agent is sodium formate. 11. Method of washing, characterized in that the stain-containing and / or soiled fabrics to be washed are brought into contact with an enzyme-containing liquid detergent comprising: (a) about 5 to about 75 wt% of one or more detergent surfactants selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergent compounds; (b) about 25 to 85% water, and (c) an enzyme mixture consisting essentially of an alkaline protease enzyme and an α-amylase enzyme in such relative amounts that the ratio of the enzyme activities is about 4,000 to about 80,000 Novo-amylse units of α-amylase per Anson unit is protease, which protease is present in an amount to provide from about 0.25 to about 2.5 Anson units per 100 g of detergent. A method according to claim 1, characterized in that the ratio of the enzyme activities in the enzyme mixture is about 15,000 to about 40,000 Novo-amylase units of α-amylase per Anson unit protease and the protease is present in such an amount that about 0.5 to about 2.0 Anson units are provided per 100 g of detergent. Method according to claim 11, characterized in that the liquid detergent mainly consists of: b o v | (a) about 20 to about 40% by weight of a nonionic detergent compound consisting essentially of a water-soluble C 1 -C 2 -alkoxy-1-C 1 -C 20 -alkanol, 5 ( b) about 4 to about 12% by weight of an anionic detergent compound consisting essentially of a water-soluble salt of a C 1 -C 5 alkylbenzene sulfonate, (c) about 3 to 15% by weight of a lower alkanol selected from the group consisting of a lower amino alcohol 1C with 1 to 4 carbon atoms, a lower polyol with 2 'to 3 carbon atoms and mixtures thereof, (d) about 0.5 to 5% by weight of an agent for controlling the viscosity, consisting essentially of a water-soluble formate salt, (e) about 35 to 65% by weight of water, and (f) an enzyme mixture consisting essentially of an alkaline protease enzyme and an α-amylase enzyme in relative amounts such that the ratio of the respective enzyme activities in the mixture 20 about 4,000 to about 80,000 Novo-amylase units α-amylase per Anson unit protease, the protease being present in an amount to provide from about 0.25 to about 2.5 Anson units per 100 detergent. 25 -w ..... f * 5 »ï