WO2004009752A1 - Alkaline liquid detergent composition - Google Patents

Alkaline liquid detergent composition Download PDF

Info

Publication number
WO2004009752A1
WO2004009752A1 PCT/KR2003/001434 KR0301434W WO2004009752A1 WO 2004009752 A1 WO2004009752 A1 WO 2004009752A1 KR 0301434 W KR0301434 W KR 0301434W WO 2004009752 A1 WO2004009752 A1 WO 2004009752A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid detergent
enzyme
detergent composition
boronic acid
sample
Prior art date
Application number
PCT/KR2003/001434
Other languages
French (fr)
Inventor
Cheol-Woo Kim
Jae-Man Kim
Woo-Hyun Kim
Myoung-Il Lee
Original Assignee
Cj Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cj Corporation filed Critical Cj Corporation
Priority to AU2003247189A priority Critical patent/AU2003247189A1/en
Publication of WO2004009752A1 publication Critical patent/WO2004009752A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/166—Organic compounds containing borium
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions

Definitions

  • the present invention relates to an alkaline liquid detergent composition, and more particularly, to an alkaline liquid detergent composition with improved enzyme storage stability by using the combination of aryl boronic acid as an enzyme inhibitor with other enzyme inhibitors.
  • a liquid detergent is easier to use than a granular detergent and has excellent solubility in cold water.
  • a liquid detergent requires a high manufacturing cost and poor detergency, when compared to a granular detergent.
  • a liquid detergent contains a large amount of contaminant degradation enzymes.
  • enzymes used in a liquid detergent composition are dissolved in high water content, together with surfactants and other types of enzymes, and thus, may easily experience the denaturation by the surfactant and autodigestion.
  • a neutral or weak alkaline (pH of about 7 to 8.5) liquid detergent composition including an enzyme stabilizer has been used. Due to such low pH, activity of an alkaline protease and detergency are lowered. Therefore, a liquid detergent has poor detergency relative to a granular detergent.
  • a boron compound has widely been known as a reversible protease inhibitor. Inhibition of a subtilisin-based serine protease by boronic acid is disclosed in Molecular & Cellular Biochemistry, 1983, 51 , pp. 5-32. In particular, Biochem. Biophys. Res. Com., 1991 , 176, pp. 401-405 discloses that boronic acid with an aromatic group such as phenyl, 4-methoxyphenyl, and 3,5-dichlorophenyl has stronger protease inhibitory activity than boronic acid with an alkyl group such as methyl, butyl, and 2-cyclohexylethyl.
  • PCT Publication WO 92/19707 discloses aryl boronic acid as a reversible subtilisin protease inhibitor and EP 0 478 050 A1 discloses a stabilization of lipase by inhibiting subtilisin protease with a boron compound.
  • compositions capable of providing enzyme stabilities by using independent boron compounds with enzyme inhibitory effects are concerned with compositions capable of providing synergistic enzyme stabilities by combination of a boron compound as an enzyme inhibitor with other enzyme inhibitors. Therefore, while searching for a method of stabilizing an enzyme at a liquid detergent with a high pH, the present inventor found an alkaline liquid detergent composition capable of maintaining enzyme stability at a pH higher than in a conventional liquid detergent. This completed the present invention.
  • the alkaline liquid detergent composition of the present invention comprises the combination of aryl boronic acid as a conventional enzyme inhibitor with other enzyme inhibitors by a predetermined ratio for enzyme stabilization.
  • the alkaline liquid detergent composition of the present invention further comprises an anionic or non-ionic surfactant and the like.
  • the present invention provides an alkaline liquid detergent composition capable of improving enzyme stability by using combinations of enzyme inhibitors.
  • a liquid detergent composition comprising: 1 to 60% by weight of a surfactant, 0.001 to 1.0% by weight of aryl boronic acid as an enzyme inhibitor, 0.1 to 20% by weight of one or more other enzyme inhibitor selected from the group consisting of formic acid, boric acid, and a salt thereof, 0.1 to 4.0% by weight of a protease, and the balance to 100% by weight being water.
  • the liquid detergent composition has an alkaline pH.
  • a surfactant as used herein may be an anionic, cationic, or non-ionic surfactant.
  • the surfactant is a non-ionic surfactant, an anionic surfactant, or a mixture thereof.
  • the non-ionic surfactant is the second widely used surfactant after anionic surfactant in the detergent industry and is a substance having a non-ionic hydrophilic group such as hydroxyl (OH) and carboxyl (RCOOR') groups. According to the shapes of a hydrophilic group, the non-ionic surfactant is classified as a polyethylene glycol type and a polyalcohol type. While the polyalcohol type surfactant is not used as a cleaning agent and a penetrating agent, the polyethylene glycol type surfactant is often used as a cleaning agent and a penetrating agent.
  • the polyethylene glycol type surfactant is prepared by adding hydrophilic ethylene oxide (CH 2 CH 2 O) to a hydrophobic raw material having a reactive hydrogen atom.
  • reactive hydrogen atom denotes a hydrogen atom present in hydroxyl (OH), carboxyl (COOH), amine (NH 2 ), or amide (CONH 2 ) groups.
  • Examples of the polyethylene glycol type surfactant to be used herein include higher alcohol-, alkyl phenyl-, fatty acid-, higher fatty acid-, aliphatic amide-, and alkanol amide-based polyethylene glycols. The general formulae of these compounds are as follows:
  • R is an alkyl group of Cs-C ⁇ 6 and n is an integer of 5 to 25.
  • R-COO-(CH 2 CH 2 0) n -H wherein, R is an alkyl group of C-io-C-ie and n is an integer of 1 to 3.
  • High aliphatic amine-based polyethylene glycol :
  • R is an alkyl group of C ⁇ o-C ⁇ 8 and n is an integer of 1 to
  • R is an alkyl group of C ⁇ 0 -C ⁇ 8 and n is an integer of 1 to
  • Alkanol amide-based polyethylene glycol wherein, R-i is an alkyl group of C- ⁇ 2 -C 20 and R 2 is an alkyl group of
  • the anionic surfactant may be alpha olefin sulfonate or its salt.
  • the alpha olefin surfactant has good biodegradability in natural state relative to a currently widely used anionic surfactant, straight alkyl benzene sulfonate and has excellent detergency and low raw material cost relative to alkyl sulfonate or alkylether sulfonate. Therefore, the alpha olefin sulfonate is the most widely used substance for a laundry detergent, together with the straight alkyl benzene sulfonate.
  • Preferred alpha olefin sulfonate contains from 10 to 18 carbon atoms in the R alkyl group.
  • the above mixture contains alkene sodium sulfonate and sodium hydroxyalkane sulfonate in a weight ratio of 7:3.
  • the anionic surfactant may also be straight alkyl benzene sulfonate, RC 6 H 4 SO 3 M wherein R is a linear alkyl group of C 12 -C- 18 , preferably C 12 -Cu, and M is a cation such as sodium, magnesium, ammonium, and substituted ammonium.
  • the anionic surfactant may be alkylsulfate, RSO 4 M, alkylether sulfate, REnSO 4 M wherein R is an alkyl group of C 12 -C 2 o, E is ethylene oxide, CH 2 CH 2 O, n is an integer of 0 to 5, and M is a cation such as sodium, magnesium, ammonium, and substituted ammonium, and fatty acid soap, RCOOM wherein R is C 12 -C 2 o and M is a cation such as sodium, magnesium, ammonium, and substituted ammonium.
  • a mixture of the anionic and non-ionic surfactants may also be used.
  • the surfactant is added in an amount of 1 to 60% by weight. If the content of the surfactant is less than 1 % by weight, the function of detergency is poor, while if it exceeds 60% by weight, it is difficult to manufacture and maintain a liquid formulation.
  • Enzyme inhibitor is added in an amount of 1 to 60% by weight. If the content of the surfactant is less than 1 % by weight, the function of detergency is poor, while if it exceeds 60% by weight, it is difficult to manufacture and maintain a liquid formulation.
  • boron compounds such as boric acid, boronic acid, borate, and boric oxide are widely used as reversible protease inhibitors.
  • boronic acid inhibits a subtilisin-based serine protease.
  • Biochem. Biophys. Res. Com., 1991 , 176, pp. 401-405 discloses that boronic acid with an aromatic group such as phenyl, 4-methoxyphenyl, and 3,5-dichlorophenyl has stronger protease inhibitory activity than boronic acid with an alkyl group such as methyl, butyl, and 2-cyclohexylethyl.
  • WO 92/19707 discloses aryl boronic acid as a reversible subtilisin protease inhibitor and EP 0 478 050 A1 discloses a boron compound as a storage stabilizer of lipase, which inhibits a subtilisin protease.
  • 3,5-dichlorophenyl boronic acid is an excellent subtilisin protease inhibitor.
  • Enzyme inhibitory activity is conventionally represented as the Ki, the dissociation constant for binding of an inhibitor to an enzyme. If the Ki is low, the inhibitor has strong inhibitory activity. Therefore, the Ki is closely related with enzyme storage stability. However, the relationship between the Ki and the enzyme storage stability are not always directly proportional.
  • these boron compounds including boronic acid bind to an active site of protease to inhibit protease activity.
  • These boron compounds inhibit activity of a protease, in particular serine protease, by covalent bonding with a serine group of the active site of the serine protease and by hydrogen bonding with a histidine group of the active site of the serine protease.
  • a boron compound with an aryl group such as phenyl boronic acid has excellent serine protease inhibitory activity due to its strong covalent bonding with a serine group of the active site of the serine protease.
  • a liquid detergent composition of the present invention comprises 0.001 to 1.0% by weight of aryl boronic acid as an enzyme inhibitor and 0.1 to 20% by weight of one or more other enzyme inhibitor selected from the group consisting of formic acid, boric acid, and a salt thereof. That is, the enzyme inhibitor as used herein is the combination of the aryl boronic acid and one or more selected from the formic acid, the boric acid, and the salt thereof. Therefore, a synergistic enzyme stabilization effect can be accomplished.
  • the aryl boronic acid may be that as represented by Formula I: Formula I
  • X and Y are independently hydrogen, C-i-C ⁇ alkyl, aryl, substituted C ⁇ -C 6 alkyl, substituted aryl, hydroxyl, hydroxyl derivative, amine, C- ⁇ -C-6 alkylated amine, amine derivative, halogen, nitro, thiol, thiol derivative, aldehyde, acid and its salt, ester, sulfonate, or phosphonate.
  • the aryl boronic acid of Formula 1 include 3-nitrophenyl boronic acid, phenyl boronic acid, and 3,5-dichlorophenyl boronic acid.
  • 3,5-dichlorophenyl boronic acid as represented by Formula 2 is used.
  • the aryl boronic acid is added in an amount of 0.001 to 1.0% by weight. If the content of the aryl boronic acid is less than 0.001 % by weight, enzyme inhibitory activity is too insignificant to accomplish a desired enzyme inhibitory effect. On the other hand, if it exceeds 1.0% by weight, an enzyme inhibitory efficiency relative to an added amount is lowered and increase of a raw material cost by excess use lowers an economical efficiency.
  • one or more other type of enzyme inhibitor selected from the group consisting of formic acid, boric acid, and a salt thereof is added in an amount of 0.1 to 20.0% by weight, more preferably 0.5 to 10% by weight. If the content of the enzyme inhibitor is less than 0.1 % by weight, it is difficult to obtain enzyme inhibitory activity, while if it exceeds 20.0% by weight, it is difficult to maintain a liquid formulation due to insufficient dissolution.
  • Protease The liquid detergent composition of the present invention comprises 0.1 to 5.0% by weight of an alkaline protease, and preferably, 0.1 to 4.0% by weight of an active protease.
  • the active protease can be derived from animals, plants, or microorganisms.
  • the active protease is a commercially available subtilisin protease such as alcalase, esperase, savinase, maxatase, maxacal, and maxapem, which is protein engineered Maxacal.
  • Alcalase, esperase, and savinase are the trade names of Novo (Denmark) and maxatase, maxacal, and maxapem are the trade names of Genenco (Italy).
  • an extracelluar alkaline protease from alkalophilic Vibrio metschnikovii strain RH530 accession number KCTC 0088BP isolated from Korean soil may be used.
  • the protease is added in an amount of 0.1 to 5.0% by weight. If the content of the protease is less than 0.1 % by weight, detergency is lowered, while if it exceeds 5.0% by weight, the function of detergency relative to an added amount is lowered. Furthermore, use of excess protease increases the added amount of the enzyme inhibitor and stabilizer therefore, thereby increasing a manufacturing cost. Therefore, use of excess protease is not preferable from an economical point of view. Enzyme stabilizer
  • the liquid detergent composition of the present invention may further comprise various ingredients, except for the above-described surfactant and enzyme inhibitors such as the aryl boronic acid, formic acid, and boric acid.
  • the liquid detergent composition of * the present invention may comprise 1 to 30% by weight, preferably 5 to 30% by weight of an enzyme stabilizer.
  • an enzyme stabilizer is used to structurally prevent the denaturation and autodigestion of enzymes and thus retard the decrease of enzyme activities.
  • a representative enzyme stabilizer is propylene glycol, ethylene glycol, and polyoxyethylene glycol. The combination of propylene glycol and ethylene glycol by an appropriate ratio was used in the Examples of the present invention below. Solubilizer
  • the liquid enzyme composition of the present invention may further comprise a solubilizer.
  • the solubilizer may be a short chain alcohol such as ethanol, ethylene glycol, and propylene glycol, or hydrotrope such as sodium cumene sulfonate, sodium xylene sulfonate, and urea.
  • the solubilizer is added in an amount of 1 to 30% by weight.
  • the liquid detergent composition of the present invention may further comprise a builder.
  • the builder is an important cleaning ingredient for a laundry detergent.
  • builder is a generic name for an alkalizing agent and a metal ion sequestrant.
  • the builder may cause problems in terms of formulation and stability when used in a liquid detergent composition, and thus, the amount used is limited.
  • the builder to be used herein is sodium carbonate, an alkalizing agent with excellent solubility, for example, sodium hydroxide, potassium hydroxide, triethanolamine, diethanolamine, and monoethanolamine.
  • the builder may be added in an amount of 5% by weight or less, preferably 1 to 3% by weight to thereby adjust pH of the composition to a desired level.
  • the liquid detergent composition of the present invention may further comprise additives as conventionally used in the pertinent art.
  • the additives include a hard water softening agent, a fluorescent whitening agent, and other types of enzymes.
  • the hard water softening agent may be trisodium nitriloacetate, tetrasodium ethylenediamine tetraacetate (EDTA 4Na), disodium ethylenediamine tetraacetate (EDTA 2Na), or sodium citrate.
  • the liquid detergent composition of the present invention may further comprise a second detergent-compatible enzyme such as amylase and cellulase as a starch degrading enzyme, lipase as a lipid degrading enzyme, oxidoreductase, and a mixture thereof, except for the above-described protease.
  • a second detergent-compatible enzyme such as amylase and cellulase as a starch degrading enzyme, lipase as a lipid degrading enzyme, oxidoreductase, and a mixture thereof, except for the above-described protease.
  • liquid detergent composition of the present invention can be prepared as follows, for example.
  • surfactant bases are prepared and then enzyme inhibitors such as sodium formate, and a boron compound including boric acid, and aryl boronic acid with varying concentrations and combination ratios are added to the surfactant bases.
  • alkalizing agents such as triethanolamine are added to adjust pH of a prepared mixture to alkaline and then proteases are added.
  • short chain alcohols or hydrotropes as used in conventional liquid detergent compositions may be added.
  • the short chain alcohols are those having carbon atoms of 1 to 5, such as ethyl alcohol, propylene glycol, isopropanol, and butanol.
  • the hydrotropes are substances generally used for viscosity adjustment or stability maintenance of detergent compositions, for example, sodium cumene sulfonate, xylene sulfonate, and urea.
  • the final pH of the liquid detergent composition of the present invention is in the range of 8.5 to 11.0. If the pH is less than 8.5, detergency is lowered, while if the pH exceeds 11.0, enzyme stability is not secured.
  • liquid detergent compositions were prepared using compositional ratios as presented in Tables 1 and 2 according to the method disclosed in the above section "Preparation procedure” and then enzyme storage stabilities were tested.
  • Enzyme storage stability was determined according to the azocasein method (Novo). Test samples of the prepared liquid detergent compositions were stored in an incubator at 40 ° C for 4 weeks and then the protease activities of the samples were measured at an interval of one week. In this case, initial measurement values were set to 100. Particularly, the test procedure was as follows:
  • azocasein a predetermined amount was dissolved in urea (50%) solution, 2M Tris (Tris(hydroxymethyl)aminomethane) buffer solution, and deionized water (D.I. water) to prepare an azocasein solution. Then, after aliquots of the test samples and the azocasein solution were incubated in a 40 ° C water bath for 30 minutes, Absorbance was measured at 390 nm using a UV spectrometer. A protein used for protease activity measurement was azocasein (Sigma). Unless particularly specified otherwise, protease used in Examples was subtilisin protease with its optimal pH of 8 to 11.
  • Table 1 Type 1 of detergent compositions with varying enzyme inhibitors
  • Table 2 Type 2 of detergent compositions with varying enzyme inhibitors
  • Comparative Example 2 Preparation of liquid detergent base of the present invention and enzvme storage stability test with varying enzyme inhibitors
  • liquid detergent compositions were prepared using compositional ratios as presented in Table 4 according to the method disclosed in the above section "Preparation procedure” and then enzyme storage stabilities were tested. Enzyme storage stabilities were determined in the same manner as in Comparative Example 1.
  • Table 4 Type 3 of detergent compositions with varying enzyme inhibitors
  • Example 1 Enzyme storage stability test with varying enzyme inhibitors
  • detergent compositions with combination of aryl boronic acid and boric acid or sodium formate were prepared according to compositional ratios of Tables 6 and 7 and then enzyme storage stabilities were determined at a high temperature.
  • Example 2 Enzyme storage stability test with varying combinations of enzyme inhibitors
  • Detergent compositions containing all of the boronic acid, sodium formate, and boric acid as enzyme inhibitors were prepared according to the compositional ratios of Tables 9 and 10 and then enzyme storage stabilities were determined at a high temperature.
  • detergent compositions with all of boronic acid, boric acid, and sodium formate, as enzyme inhibitors maintained average 60% or more of enzyme activities after 4 weeks, which are excellent results when compared to the above-obtained test results.
  • Example 3 Enzyme storage stability test with increase of boronic acid
  • Detergent compositions with increase of boronic acid were prepared according to the compositional ratio of Table 12 and then enzyme storage stabilities were determined at a high temperature.
  • Detergent compositions with varying types and contents of surfactants were prepared according to the compositional ratios of Table 14 and then enzyme storage stabilities were determined at a high temperature.
  • Table 14 Type 1 of detergent compositions with varying types and contents of surfactants
  • detergent compositions with anionic surfactants exhibited slightly low enzyme activities, when compared to those with mainly non-ionic surfactants. However, all of the detergent compositions exhibited 60% or more of enzyme activities after 4 weeks.
  • Example 5 Type 2 of enzyme storage stability test with varying types and contents of surfactants Detergent compositions with varying types and contents of surfactants were prepared according to the compositional ratios of Table 16 and then enzyme storage stabilities were determined at a high temperature.
  • Table 16 Type 2 of detergent compositions with varying types and contents of surfactants
  • liquid detergent composition of the present invention has considerably improved enzyme storage stability by combination of aryl boronic acid with formic acid and/or boric acid.

Abstract

Provided is a liquid detergent composition. The liquid detergent composition includes 1 to 60% by weight of a surfactant, 0.001 to 1.0% by weight of aryl boronic acid as an enzyme inhibitor, 0.1 to 20% by weight of one or more other enzyme inhibitor selected from the group consisting of formic acid, boric acid, and a salt thereof,0.1 to 4.0% by weight of a protease, and the balance to 100% by weight being water, and has an alkaline pH. The liquid detergent composition has considerably improved enzyme storage stability by combination of aryl boronic acid with formic acid and/or boric acid.

Description

ALKALINE LIQUID DETERGENT COMPOSITION
Technical Field The present invention relates to an alkaline liquid detergent composition, and more particularly, to an alkaline liquid detergent composition with improved enzyme storage stability by using the combination of aryl boronic acid as an enzyme inhibitor with other enzyme inhibitors.
Background Art
A liquid detergent is easier to use than a granular detergent and has excellent solubility in cold water. However, a liquid detergent requires a high manufacturing cost and poor detergency, when compared to a granular detergent. In order to solve these disadvantages, a liquid detergent contains a large amount of contaminant degradation enzymes. However, such enzymes used in a liquid detergent composition are dissolved in high water content, together with surfactants and other types of enzymes, and thus, may easily experience the denaturation by the surfactant and autodigestion. In addition, it is difficult to preserve the storage stability of the enzymes from the pH of a liquid detergent composition.
Conventionally, in order to stabilize an enzyme in a liquid detergent composition, a neutral or weak alkaline (pH of about 7 to 8.5) liquid detergent composition including an enzyme stabilizer has been used. Due to such low pH, activity of an alkaline protease and detergency are lowered. Therefore, a liquid detergent has poor detergency relative to a granular detergent.
Meanwhile, a boron compound has widely been known as a reversible protease inhibitor. Inhibition of a subtilisin-based serine protease by boronic acid is disclosed in Molecular & Cellular Biochemistry, 1983, 51 , pp. 5-32. In particular, Biochem. Biophys. Res. Com., 1991 , 176, pp. 401-405 discloses that boronic acid with an aromatic group such as phenyl, 4-methoxyphenyl, and 3,5-dichlorophenyl has stronger protease inhibitory activity than boronic acid with an alkyl group such as methyl, butyl, and 2-cyclohexylethyl. In addition, PCT Publication WO 92/19707 discloses aryl boronic acid as a reversible subtilisin protease inhibitor and EP 0 478 050 A1 discloses a stabilization of lipase by inhibiting subtilisin protease with a boron compound.
However, the above-described documents are concerned with compositions capable of providing enzyme stabilities by using independent boron compounds with enzyme inhibitory effects. Unlike the present invention, there are no disclosures or discussions about compositions capable of providing synergistic enzyme stabilities by combination of a boron compound as an enzyme inhibitor with other enzyme inhibitors. Therefore, while searching for a method of stabilizing an enzyme at a liquid detergent with a high pH, the present inventor found an alkaline liquid detergent composition capable of maintaining enzyme stability at a pH higher than in a conventional liquid detergent. This completed the present invention. The alkaline liquid detergent composition of the present invention comprises the combination of aryl boronic acid as a conventional enzyme inhibitor with other enzyme inhibitors by a predetermined ratio for enzyme stabilization. In addition to these enzyme inhibitors, the alkaline liquid detergent composition of the present invention further comprises an anionic or non-ionic surfactant and the like.
Disclosure of the Invention
The present invention provides an alkaline liquid detergent composition capable of improving enzyme stability by using combinations of enzyme inhibitors. According to an aspect of the present invention, there is provided a liquid detergent composition comprising: 1 to 60% by weight of a surfactant, 0.001 to 1.0% by weight of aryl boronic acid as an enzyme inhibitor, 0.1 to 20% by weight of one or more other enzyme inhibitor selected from the group consisting of formic acid, boric acid, and a salt thereof, 0.1 to 4.0% by weight of a protease, and the balance to 100% by weight being water. The liquid detergent composition has an alkaline pH.
Best mode for carrying out the Invention Surfactant
A surfactant as used herein may be an anionic, cationic, or non-ionic surfactant. Preferably, the surfactant is a non-ionic surfactant, an anionic surfactant, or a mixture thereof. The non-ionic surfactant is the second widely used surfactant after anionic surfactant in the detergent industry and is a substance having a non-ionic hydrophilic group such as hydroxyl (OH) and carboxyl (RCOOR') groups. According to the shapes of a hydrophilic group, the non-ionic surfactant is classified as a polyethylene glycol type and a polyalcohol type. While the polyalcohol type surfactant is not used as a cleaning agent and a penetrating agent, the polyethylene glycol type surfactant is often used as a cleaning agent and a penetrating agent.
The polyethylene glycol type surfactant is prepared by adding hydrophilic ethylene oxide (CH2CH2O) to a hydrophobic raw material having a reactive hydrogen atom. As used herein, the term, reactive hydrogen atom denotes a hydrogen atom present in hydroxyl (OH), carboxyl (COOH), amine (NH2), or amide (CONH2) groups. Examples of the polyethylene glycol type surfactant to be used herein include higher alcohol-, alkyl phenyl-, fatty acid-, higher fatty acid-, aliphatic amide-, and alkanol amide-based polyethylene glycols. The general formulae of these compounds are as follows:
Higher alcohol-based polyethylene glycol:
R-0-(CH2CH20)n-H wherein, R is an alkyl group of Cβ-Ciβ and n is an integer of 5 to
25.
Alkylphenyl-based polyethylene glycol:
Figure imgf000005_0001
wherein, R is an alkyl group of Cs-Cι6 and n is an integer of 5 to 25.
Fatty acid-based polyethylene glycol:
R-COO-(CH2CH20)n-H wherein, R is an alkyl group of C-io-C-ie and n is an integer of 1 to 3. High aliphatic amine-based polyethylene glycol:
Figure imgf000005_0002
wherein, R is an alkyl group of Cιo-Cι8 and n is an integer of 1 to
Aliphatic amide-based polyethylene glycol:
Figure imgf000005_0003
wherein, R is an alkyl group of Cι0-Cι8 and n is an integer of 1 to
Alkanol amide-based polyethylene glycol:
Figure imgf000005_0004
wherein, R-i is an alkyl group of C-ι2-C20 and R2 is an alkyl group of
Cι-C2.
The anionic surfactant may be alpha olefin sulfonate or its salt. The alpha olefin surfactant has good biodegradability in natural state relative to a currently widely used anionic surfactant, straight alkyl benzene sulfonate and has excellent detergency and low raw material cost relative to alkyl sulfonate or alkylether sulfonate. Therefore, the alpha olefin sulfonate is the most widely used substance for a laundry detergent, together with the straight alkyl benzene sulfonate. The alpha olefin sulfonate includes long-chain alkene sulfonate(RCH=CHCH2SO3 ") and its salt, long-chain hydroxyalkane sulfonate(RCHOHCH2CH2SO3 ") or its salt or a mixture of alkene sulfonate and hydroxyalkane sulfonate such as a mixture of alkene sodium sulfonate(RCH=CHCH2SO3Na) and sodium hydroxyalkane sulfonate(RCHOHCH2CH2SO3Na). Preferred alpha olefin sulfonate contains from 10 to 18 carbon atoms in the R alkyl group. Preferably, the above mixture contains alkene sodium sulfonate and sodium hydroxyalkane sulfonate in a weight ratio of 7:3. The anionic surfactant may also be straight alkyl benzene sulfonate, RC6H4SO3M wherein R is a linear alkyl group of C12-C-18, preferably C12-Cu, and M is a cation such as sodium, magnesium, ammonium, and substituted ammonium.
In addition, the anionic surfactant may be alkylsulfate, RSO4M, alkylether sulfate, REnSO4M wherein R is an alkyl group of C12-C2o, E is ethylene oxide, CH2CH2O, n is an integer of 0 to 5, and M is a cation such as sodium, magnesium, ammonium, and substituted ammonium, and fatty acid soap, RCOOM wherein R is C12-C2o and M is a cation such as sodium, magnesium, ammonium, and substituted ammonium. A mixture of the anionic and non-ionic surfactants may also be used.
Preferably, the surfactant is added in an amount of 1 to 60% by weight. If the content of the surfactant is less than 1 % by weight, the function of detergency is poor, while if it exceeds 60% by weight, it is difficult to manufacture and maintain a liquid formulation. Enzyme inhibitor
Generally, boron compounds such as boric acid, boronic acid, borate, and boric oxide are widely used as reversible protease inhibitors. By way of examples, Molecular & Cellular Biochemistry, 1983, 51 , pp. 5-32 discloses that boronic acid inhibits a subtilisin-based serine protease. In particular, Biochem. Biophys. Res. Com., 1991 , 176, pp. 401-405 discloses that boronic acid with an aromatic group such as phenyl, 4-methoxyphenyl, and 3,5-dichlorophenyl has stronger protease inhibitory activity than boronic acid with an alkyl group such as methyl, butyl, and 2-cyclohexylethyl. In addition, WO 92/19707 discloses aryl boronic acid as a reversible subtilisin protease inhibitor and EP 0 478 050 A1 discloses a boron compound as a storage stabilizer of lipase, which inhibits a subtilisin protease. In particular, 3,5-dichlorophenyl boronic acid is an excellent subtilisin protease inhibitor.
Enzyme inhibitory activity is conventionally represented as the Ki, the dissociation constant for binding of an inhibitor to an enzyme. If the Ki is low, the inhibitor has strong inhibitory activity. Therefore, the Ki is closely related with enzyme storage stability. However, the relationship between the Ki and the enzyme storage stability are not always directly proportional.
It is known that these boron compounds including boronic acid bind to an active site of protease to inhibit protease activity. These boron compounds inhibit activity of a protease, in particular serine protease, by covalent bonding with a serine group of the active site of the serine protease and by hydrogen bonding with a histidine group of the active site of the serine protease. In particular, it is known that a boron compound with an aryl group such as phenyl boronic acid has excellent serine protease inhibitory activity due to its strong covalent bonding with a serine group of the active site of the serine protease.
A liquid detergent composition of the present invention comprises 0.001 to 1.0% by weight of aryl boronic acid as an enzyme inhibitor and 0.1 to 20% by weight of one or more other enzyme inhibitor selected from the group consisting of formic acid, boric acid, and a salt thereof. That is, the enzyme inhibitor as used herein is the combination of the aryl boronic acid and one or more selected from the formic acid, the boric acid, and the salt thereof. Therefore, a synergistic enzyme stabilization effect can be accomplished.
The aryl boronic acid may be that as represented by Formula I: Formula I
Figure imgf000008_0001
wherein, X and Y are independently hydrogen, C-i-Cβ alkyl, aryl, substituted Cι-C6 alkyl, substituted aryl, hydroxyl, hydroxyl derivative, amine, C-ι-C-6 alkylated amine, amine derivative, halogen, nitro, thiol, thiol derivative, aldehyde, acid and its salt, ester, sulfonate, or phosphonate. Examples of the aryl boronic acid of Formula 1 include 3-nitrophenyl boronic acid, phenyl boronic acid, and 3,5-dichlorophenyl boronic acid. Preferably, 3,5-dichlorophenyl boronic acid as represented by Formula 2 is used.
Figure imgf000008_0002
Preferably, the aryl boronic acid is added in an amount of 0.001 to 1.0% by weight. If the content of the aryl boronic acid is less than 0.001 % by weight, enzyme inhibitory activity is too insignificant to accomplish a desired enzyme inhibitory effect. On the other hand, if it exceeds 1.0% by weight, an enzyme inhibitory efficiency relative to an added amount is lowered and increase of a raw material cost by excess use lowers an economical efficiency.
Preferably, one or more other type of enzyme inhibitor selected from the group consisting of formic acid, boric acid, and a salt thereof is added in an amount of 0.1 to 20.0% by weight, more preferably 0.5 to 10% by weight. If the content of the enzyme inhibitor is less than 0.1 % by weight, it is difficult to obtain enzyme inhibitory activity, while if it exceeds 20.0% by weight, it is difficult to maintain a liquid formulation due to insufficient dissolution. Protease The liquid detergent composition of the present invention comprises 0.1 to 5.0% by weight of an alkaline protease, and preferably, 0.1 to 4.0% by weight of an active protease. The active protease can be derived from animals, plants, or microorganisms. More preferably, the active protease is a commercially available subtilisin protease such as alcalase, esperase, savinase, maxatase, maxacal, and maxapem, which is protein engineered Maxacal. Alcalase, esperase, and savinase are the trade names of Novo (Denmark) and maxatase, maxacal, and maxapem are the trade names of Genenco (Italy). In addition, an extracelluar alkaline protease from alkalophilic Vibrio metschnikovii strain RH530 (accession number KCTC 0088BP) isolated from Korean soil may be used.
Preferably, as used herein, the protease is added in an amount of 0.1 to 5.0% by weight. If the content of the protease is less than 0.1 % by weight, detergency is lowered, while if it exceeds 5.0% by weight, the function of detergency relative to an added amount is lowered. Furthermore, use of excess protease increases the added amount of the enzyme inhibitor and stabilizer therefore, thereby increasing a manufacturing cost. Therefore, use of excess protease is not preferable from an economical point of view. Enzyme stabilizer
The liquid detergent composition of the present invention may further comprise various ingredients, except for the above-described surfactant and enzyme inhibitors such as the aryl boronic acid, formic acid, and boric acid. For example, the liquid detergent composition of * the present invention may comprise 1 to 30% by weight, preferably 5 to 30% by weight of an enzyme stabilizer. Generally, in the case of enzymes used in a liquid detergent composition, enzyme activities decrease by denaturation or autodigestion with time. The enzyme stabilizer is used to structurally prevent the denaturation and autodigestion of enzymes and thus retard the decrease of enzyme activities. A representative enzyme stabilizer is propylene glycol, ethylene glycol, and polyoxyethylene glycol. The combination of propylene glycol and ethylene glycol by an appropriate ratio was used in the Examples of the present invention below. Solubilizer
The liquid enzyme composition of the present invention may further comprise a solubilizer. The solubilizer may be a short chain alcohol such as ethanol, ethylene glycol, and propylene glycol, or hydrotrope such as sodium cumene sulfonate, sodium xylene sulfonate, and urea. Preferably, the solubilizer is added in an amount of 1 to 30% by weight.
Builder The liquid detergent composition of the present invention may further comprise a builder. The builder is an important cleaning ingredient for a laundry detergent. Generally, the term, builder is a generic name for an alkalizing agent and a metal ion sequestrant. The builder may cause problems in terms of formulation and stability when used in a liquid detergent composition, and thus, the amount used is limited. The builder to be used herein is sodium carbonate, an alkalizing agent with excellent solubility, for example, sodium hydroxide, potassium hydroxide, triethanolamine, diethanolamine, and monoethanolamine. The builder may be added in an amount of 5% by weight or less, preferably 1 to 3% by weight to thereby adjust pH of the composition to a desired level.
Other than the above-described ingredients, the liquid detergent composition of the present invention may further comprise additives as conventionally used in the pertinent art. Examples of the additives include a hard water softening agent, a fluorescent whitening agent, and other types of enzymes. The hard water softening agent may be trisodium nitriloacetate, tetrasodium ethylenediamine tetraacetate (EDTA 4Na), disodium ethylenediamine tetraacetate (EDTA 2Na), or sodium citrate. The liquid detergent composition of the present invention may further comprise a second detergent-compatible enzyme such as amylase and cellulase as a starch degrading enzyme, lipase as a lipid degrading enzyme, oxidoreductase, and a mixture thereof, except for the above-described protease.
Preparation procedure
The liquid detergent composition of the present invention can be prepared as follows, for example.
First, surfactant bases are prepared and then enzyme inhibitors such as sodium formate, and a boron compound including boric acid, and aryl boronic acid with varying concentrations and combination ratios are added to the surfactant bases. Next, alkalizing agents such as triethanolamine are added to adjust pH of a prepared mixture to alkaline and then proteases are added. When an adjustment of the viscosity of the obtained mixture is required, short chain alcohols or hydrotropes as used in conventional liquid detergent compositions may be added. Herein, the short chain alcohols are those having carbon atoms of 1 to 5, such as ethyl alcohol, propylene glycol, isopropanol, and butanol. The hydrotropes are substances generally used for viscosity adjustment or stability maintenance of detergent compositions, for example, sodium cumene sulfonate, xylene sulfonate, and urea.
Preferably, the final pH of the liquid detergent composition of the present invention is in the range of 8.5 to 11.0. If the pH is less than 8.5, detergency is lowered, while if the pH exceeds 11.0, enzyme stability is not secured.
Examples
Hereinafter, the present invention will be described more specifically by examples. However, the following examples are provided only for illustrations and thus the present invention is not limited to or by them. The alpha olefin sulfonate used in the Examples hereinafter was a mixture of alkene sodium sulfonate and hydroxyalkane sodium sulfonate which was commercially available. Comparative Example 1 : Preparation of liquid detergent base of the present invention and enzyme storage stability test with varying enzyme inhibitors
In this Example, liquid detergent compositions were prepared using compositional ratios as presented in Tables 1 and 2 according to the method disclosed in the above section "Preparation procedure" and then enzyme storage stabilities were tested.
1. Enzyme storage stability test
Enzyme storage stability was determined according to the azocasein method (Novo). Test samples of the prepared liquid detergent compositions were stored in an incubator at 40 °C for 4 weeks and then the protease activities of the samples were measured at an interval of one week. In this case, initial measurement values were set to 100. Particularly, the test procedure was as follows:
First, a predetermined amount of azocasein was dissolved in urea (50%) solution, 2M Tris (Tris(hydroxymethyl)aminomethane) buffer solution, and deionized water (D.I. water) to prepare an azocasein solution. Then, after aliquots of the test samples and the azocasein solution were incubated in a 40 °C water bath for 30 minutes, Absorbance was measured at 390 nm using a UV spectrometer. A protein used for protease activity measurement was azocasein (Sigma). Unless particularly specified otherwise, protease used in Examples was subtilisin protease with its optimal pH of 8 to 11.
Table 1 : Type 1 of detergent compositions with varying enzyme inhibitors
Ingredients Sample 1 Sample 2 Sample 3 Sample 4
Polyoxyethylene alkyl , 30.0 30.0 30.0 30.0 ether (EO=7 mole)
Straight alkylbenzene 6.0 6.0 6.0 6.0 sulfonate
Alpha olefin sulfonate 3.0 3.0 3.0 3.0
Alkyl ether sulfate 5.0 5.0 5.0 5.0
Ethylene glycol 5.0 5.0 5.0 5.0
Propylene glycol 20.0 20.0 20.0 20.0
Ethyl alcohol 5.0 5.0 5.0 5.0
Sodium xylene sulfonate 2.0 2.0 2.0 2.0
Monoethanolamine 4.0 4.0 4.0 4.0
EDTA 4Na 0.2 0.2 0.2 0.2
3-Nitrophenyl boronic acid 0.1
Phenyl boronic acid 0.1
3,5-Dichlorophenyl 0.1 boronic acid
Protease 0.6 0.6 0.6 0.6
D.I. water Balance* Balance Balance Balance
Total 100 100 100 100
Unit % by weight
*Balance means the amount of D.I. water to make up 100% and is used as the same meaning in the following Tables.
Table 2: Type 2 of detergent compositions with varying enzyme inhibitors
Ingredients Sample 5 Sample 6 Sample 7 Sample 8
Polyoxyethylene alkyl ether 35.0 35.0 35.0 35.0
(EO = 9 mole)
Propylene glycol 25.0 25.0 25.0 25.0
Ethyl alcohol 5.0 5.0 5.0 5.0
Sodium xylene sulfonate 2.0 2.0 2.0 2.0
Monoethanolamine 4.0 4.0 4.0 4.0
EDTA 4Na 0.2 0.2 0.2 0.2
3-Nitrophenyl boronic acid 0.1
Phenyl boronic acid 0.1
3,5-Dichlorophenyl boronic acid 0.1
Protease 0.6 0.6 0.6 0.6
D.I. water Balance Balance Balance Balance
Total 100 100 100 100
Unit: % by weight
Table 3: Enzyme activities at high temperature with time
Sample Initial 1 week 2 weeks 3 weeks 4 weeks
Sample 1 100 79 71 58 39
Sample 2 100 81 67 55 36
Sample 3 100 73 65 55 39
Sample 4 100 70 59 42 30
Sample 5 100 76 66 51 39
Sample 6 100 74 66 56 38
Sample 7 100 72 63 49 40
Sample 8 100 70 55 40 26
From the results as shown in Table 3, it can be seen that boronic acid-containing detergent compositions have excellent enzyme storage stabilities, when compared to boronic acid-free detergent compositions. However, after 4 weeks, protease activities of all the detergent compositions were reduced to less than 50%.
Comparative Example 2: Preparation of liquid detergent base of the present invention and enzvme storage stability test with varying enzyme inhibitors
In this Example, liquid detergent compositions were prepared using compositional ratios as presented in Table 4 according to the method disclosed in the above section "Preparation procedure" and then enzyme storage stabilities were tested. Enzyme storage stabilities were determined in the same manner as in Comparative Example 1.
Table 4: Type 3 of detergent compositions with varying enzyme inhibitors
Ingredients Sample Sample Sample Sample Sample
9 10 11 12 13
Polyoxyethylene alkyl 26.0 21.0 35.0 28.0 30.0 ether (EO=9mole)
Propylene glycol 10.0 5.0 25.0 17.0 21.0
Ethyl alcohol 5.0 3.0 5.0 3.7 3.0
Sodium xylene sulfonate 2.0 0.0 2.0 2.0 2.0
Monoethanolamine 3.3 4.0 3.0 3.0 3.0
EDTA 4Na 0.2 0.2 0.2 0.2 0.2
Boric acid 0.6 1.2 0.6
Sodium formate 1.0 1.5 1.0
Calcium chloride 0.07 0.07 0.07 0.07 0.07
Protease 0.6 0.6 0.6 0.6 0.6
D.I. water Balance Balance Balance Balance Balance
Total 100 100 100 100 100
Unit: % by weight
Table 5: Enzyme activities at high temperature with time
Sample Initial 1 week 2 weeks 3 weeks 4 weeks
Sample 9 100 76 56 37 29
Sample 10 100 70 49 32 20
Sample 1 1 100 73 53 35 24
Sample 12 100 73 50 36 30
Sample 13 100 75 61 42 33
As shown in Table 5, all the detergent compositions of samples 9 through 13 had lower enzyme storage stabilities than the boronic acid-containing detergent compositions of Table 3. Furthermore, there were little differences between the enzyme stabilities of all the detergent compositions of samples 9 through 13 and the boronic acid-free detergent compositions of Table 3.
Example 1 : Enzyme storage stability test with varying enzyme inhibitors
In this Example, enzyme storage stabilities of detergent compositions with combination of aryl boronic acid and other types of protease inhibitors were determined.
For this, detergent compositions with combination of aryl boronic acid and boric acid or sodium formate were prepared according to compositional ratios of Tables 6 and 7 and then enzyme storage stabilities were determined at a high temperature.
Table 6: Detergent compositions with varying concentrations of boric acid
Ingredients Sample Sample Sample Sample
14 15 16 17
Polyoxyethylene alkyl ether 30.0 30.0 30.0 30.0
(EO=7 mole)
Straight alkylbenzene sulfonate 6.0 6.0 6.0 6.0
Alpha olefin sulfonate 3.0 3.0 3.0 3.0
Alkyl ether sulfate 5.0 5.0 5.0 5.0
Ethylene glycol 5.0 5.0 5.0 5.0
Propylene glycol 20.0 20.0 20.0 20.0
Ethyl alcohol 5.0 5.0 5.0 5.0
Sodium xylene sulfonate 2.0 2.0 2.0 2.0
Monoethanolamine 4.0 4.0 4.0 4.0
EDTA 4Na 0.2 0.2 0.2 0.2
3-Nitrophenyl boronic acid 0.1 0.1 0.1 0.1
Boric acid 0.5 1.0 1.5 2.0
Protease 0.9 0.9 0.9 0.9
D.I. water Balance Balance Balance Balance
Total 100 100 100 100
Unit: % by weight
Table 7: Detergent compositions with varying concentrations of sodium formate
Ingredients Sample 18 Sample 19 Sample 20 Sample 21
Polyoxyethylene alkyl 30.0 30.0 30.0 30.0 ether (EO=7 mole)
Straight alkylbenzene 6.0 6.0 6.0 6.0 sulfonate
Alpha olefin sulfonate 3.0 3.0 3.0 3.0
Alkyl ether sulfate 5.0 5.0 5.0 5.0
Ethylene glycol 5.0 5.0 5.0 5.0
Propylene glycol 20.0 20.0 20.0 20.0
Ethyl alcohol 5.0 5.0 5.0 5.0
Sodium xylene sulfonate 2.0 2.0 2.0 2.0
Monoethanolamine 4.0 4.0 4.0 4.0
EDTA 4Na 0.2 0.2 0.2 0.2
Phenyl boronic acid 0.1 0.1 0.1 0.1
Sodium formate 0.5 1.0 1.5 2.0
Protease 0.9 0.9 0.9 0.9
D.I. water Balance Balance Balance Balance
Total 100 100 100 100
Unit: % by weight
Table 8: Enzyme activities at high temperature with time
Sample Initial 1 week 2 weeks 3 weeks 4 weeks
Sample 14 100 80 72 67 52
Sample 15 100 83 75 67 52
Sample 16 100 85 77 71 55
Sample 17 100 90 77 69 59
Sample 18 100 85 80 70 50
Sample 19 100 90 84 65 53
Sample 20 100 93 87 70 53
Sample 21 100 91 85 71 52
From the results as shown in Table 8, it can be seen that the detergent compositions with combination of boronic acid and boric acid or sodium formate have excellent enzyme storage stabilities, when compared to the compositions of Tables 3 and 5.
Example 2: Enzyme storage stability test with varying combinations of enzyme inhibitors Detergent compositions containing all of the boronic acid, sodium formate, and boric acid as enzyme inhibitors were prepared according to the compositional ratios of Tables 9 and 10 and then enzyme storage stabilities were determined at a high temperature.
Table 9: Detergent compositions containing all of boronic acid, sodium formate, and boric acid, as enzyme inhibitors
Ingredients Sample 22 Sample 23 Sample 24
Polyoxyethylene alkyl ether 30.0 30.0 30.0
(EO=7 mole)
Straight alkylbenzene sulfonate 6.0 6.0 6.0
Alpha olefin sulfonate 3.0 3.0 3.0
Alkyl ether sulfate 5.0 5.0 5.0
Ethylene glycol 5.0 5.0 5.0
Propylene glycol 20.0 20.0 20.0
Ethyl alcohol 5.0 5.0 5.0
Sodium xylene sulfonate 2.0 2.0 2.0
Monoethanolamine 4.0 4.0 4.0
EDTA 4Na 0.2 0.2 0.2
Phenyl boronic acid 0.2 0.2 0.2
Boric acid 0.5 0.5 0.5
Sodium formate 1.0 1.5 2.0
Protease 0.9 0.9 0.9
D.I. water Balance Balance Balance
Total 100 100 100
Unit: % by weight Table 10: Detergent compositions containing all of boronic acid, sodium formate, and boric acid, as enzyme inhibitors
Ingredients Sample Sample Sample Sample
25 26 27 28
Polyoxyethylene alkyl ether 30.0 30.0 30.0 30.0
(EO=7 mole)
Straight alkylbenzene sulfonate 6.0 6.0 6.0 6.0
Alpha olefin sulfonate 3.0 3.0 3.0 3.0
Alkyl ether sulfate 5.0 5.0 5.0 5.0
Ethylene glycol 5.0 5.0 5.0 5.0
Propylene glycol 20.0 20.0 20.0 20.0
Ethyl alcohol 5.0 5.0 5.0 5.0
Sodium xylene sulfonate 2.0 2.0 2.0 2.0
Monoethanolamine 4.0 4.0 4.0 4.0
EDTA 4Na 0.2 0.2 0.2 0.2
Phenyl boronic acid 0.2 0.2 0.2 0.2
Boric acid 0.3 0.6 0.9 1.2
Sodium formate 1.0 1.0 1.0 1.0
Protease 0.9 0.9 0.9 0.9
D.I. water Balance Balance Balance Balance
Total 100 100 100 100
Unit: % by weight
Table 11 : Enzyme activities at high temperature with time
Sample Initial 1 week 2 weeks 3 weeks 4 weeks
Sample 22 100 90 85 73 59
Sample 23 100 92 90 77 63
Sample 24 100 95 90 81 67
Sample 25 100 85 81 70 60
Sample 26 100 95 85 78 65
Sample 27 100 94 86 75 65
Sample 28 100 96 90 79 69
As shown in Table 11 , detergent compositions with all of boronic acid, boric acid, and sodium formate, as enzyme inhibitors, maintained average 60% or more of enzyme activities after 4 weeks, which are excellent results when compared to the above-obtained test results.
Example 3: Enzyme storage stability test with increase of boronic acid
Detergent compositions with increase of boronic acid were prepared according to the compositional ratio of Table 12 and then enzyme storage stabilities were determined at a high temperature.
Table 12: Detergent compositions with increase of boronic acid
Ingredients Sample 29 Sample 30 Sample 31 Sample 32
Polyoxyethylene alkyl ether (EO=7 mole) 5.0 5.0 5.0 5.0
Polyoxyethylene alkyl ether (EO=9 mole) 13.0 13.0 13.0 13.0
Polyoxyethylene alkylphenyl ether 2.0 2.0 2.0 2.0
(EO=9 mole)
Straight alkylbenzene sulfonate 6.0 6.0 6.0 6.0
Alpha olefin sulfonate 5.0 5.0 5.0 5.0
Alkyl ether sulfate 5.0 5.0 5.0 5.0
Ethylene glycol 5.0 5.0 5.0 5.0
Propylene glycol 20.0 20.0 20.0 20.0
Ethyl alcohol 5.0 5.0 5.0 5.0
Sodium xylene sulfonate 2.0 2.0 2.0 2.0
Monoethanolamine 4.0 4.0 4.0 4.0
EDTA 4Na 0.2 0.2 0.2 0.2
3-Nitrophenyl boronic acid 0.5 1.0
Phenyl boronic acid 0.5 1.0
Boric acid 0.6 0.6 0.6 0.6
Sodium formate 1.3 1.3 1.3 1.3
Protease 0.9 0.9 0.9 0.9
D.I. water Balance Balance Balance Balance
Total 100 100 100 100
Unit: % by weight
Table 13: Enzyme activities at high temperature after 4 weeks
Sample Initial 4 weeks
Sample 29 Ϊ0O 65
Sample 30 100 68
Sample 31 100 70
Sample 32 100 68 As shown in Table 13, enzyme storage stabilities were slightly changed depending on the concentration of boronic acid within a specific concentration range of boronic acid. Example 4: Type 1 of enzyme storage stability test with varying types and contents of surfactants
Detergent compositions with varying types and contents of surfactants were prepared according to the compositional ratios of Table 14 and then enzyme storage stabilities were determined at a high temperature.
Table 14: Type 1 of detergent compositions with varying types and contents of surfactants
Ingredients Sample 33 Sample 34 Sample 35 Sample 36
Polyoxyethylene alkyl ether (E0=7 mole) 15.0
Polyoxyethylene alkyl ether (E0=9 mole) 13.0 7.0
Polyoxyethylene alkylphenyl ether 3.0
(E0=7 mole)
Polyoxyethylene alkylphenyl ether 20.0
(EO=9 mole)
Straight alkylbenzene sulfonate 15.0 20.0 2.0
Alpha olefin sulfonate 5.0 10.0 10.0
Alkyl ether sulfate 5.0 10.0 10.0
Alkyl sulfate 1.0
Ethylene glycol 5.0 5.0 5.0 3.0
Propylene glycol 20.0 20.0 20.0 18.0
Ethyl alcohol 5.0 5.0 5.0 3.0
Sodium xylene sulfonate 2.0 2.0 2.0
Monoethanolamine 4.0 3.0 3.0 4.0
Sodium carbonate 1.0 1.0
Phenyl boronic acid 0.2 0.2 0.2 0.2
Boric acid 0.8 0.8 0.8 0.8
Sodium formate 1.3 1.3 1.3 1.3
Protease 0.9 0.9 0.9 0.9
D.I. water Balance Balance Balance Balance
Total 100 100 100 100
Unit: % by weight
Table 15: Enzyme activities at high temperature with time
Sample Initial 1 week 2 weeks 3 weeks 4 weeks
Sample 33 100 93 82 77 69
Sample 34 100 85 76 70 63
Sample 35 100 80 71 65 60
Sample 36 100 90 85 75 66
As shown in Table 15, detergent compositions with anionic surfactants exhibited slightly low enzyme activities, when compared to those with mainly non-ionic surfactants. However, all of the detergent compositions exhibited 60% or more of enzyme activities after 4 weeks.
Example 5: Type 2 of enzyme storage stability test with varying types and contents of surfactants Detergent compositions with varying types and contents of surfactants were prepared according to the compositional ratios of Table 16 and then enzyme storage stabilities were determined at a high temperature.
Table 16: Type 2 of detergent compositions with varying types and contents of surfactants
Ingredients Sample Sample Sample Sample
37 38 39 40
Polyoxyethylene alkyl ether 13.0 7.0 27.0
(EO=9 mole)
Straight alkylbenzene sulfonate 20.0
Alpha olefin sulfonate 5.0 10.0
Alkyl ether sulfate 5.0 10.0 10.0
Alkyl sulfate 1.0
Ethylene glycol 5.0 5.0
Propylene glycol 20.0 12.0 13.0 13.0
Ethyl alcohol 5.0 3.0
Sodium xylene sulfonate 2.0 1.0 2.0 2.0
Monoethanolamine 4.0 3.0 3.0 3.0
Sodium carbonate 1.0
Phenyl boronic acid 0.1 0.1 0.1 0.1
Boric acid 0.8 0.8 0.8 0.8
Sodium formate 1.3 1.3 1.3 1.3
Protease* 0.9 0.9 0.9 0.9
D.I. water Balance Balance Balance Balance
Total 100 100 100 100
Unit: % by weight
*Proteases: an extraceliuar alkaline protease from aikalophilic Vibrio metschnikovii strain
RH530 (accession number KCTC 0088BP) isolated from Korean soil
Table 17: Enzyme activities at high temperature with time
Sample Initial 1 week 2 weeks 3 weeks 4 weeks
Sample 37 100 92 85 75 65
Sample 38 100 83 72 63 59
Sample 39 100 83 71 60 53
Sample 40 100 94 87 70 63
As shown in Table 17, as the content of water decreases, enzyme stabilities increase, and vice versa. However, detergent compositions with low water contents exhibited still considerable enzyme stabilities. Industrial Applicability
As apparent from the above description, the liquid detergent composition of the present invention has considerably improved enzyme storage stability by combination of aryl boronic acid with formic acid and/or boric acid.

Claims

What is claimed is:
1. An alkaline liquid detergent composition comprising: 1 to 60% by weight of a surfactant, 0.001 to 1.0% by weight of aryl boronic acid as an enzyme inhibitor, 0.1 to 20% by weight of one or more other enzyme inhibitor selected from the group consisting of formic acid, boric acid, and a salt thereof, 0.1 to 5.0% by weight of a protease, and the balance to 100% by weight being water.
2. The liquid detergent composition according to claim 1 , wherein the surfactant is a non-ionic surfactant, an anionic surfactant, or a mixture thereof.
3. The liquid detergent composition according to claim 2, wherein the non-ionic surfactant is polyoxyethylene alkyl ether,
R-0-(CH2CH20)n-H u . „ . „ , wherein R is an alkyl group of Ca-Ci6 and n is an integer of 5 to 25; or polyoxyethylene alkylphenyl ether,
Figure imgf000027_0001
wherein R is an alkyl group of
C8-Ci6 and n is an integer of 5 to 25; and the anionic surfactant is alpha olefin sulfonate; straight alkyl benzene sulfonate, RC-6H SO3M wherein R is a linear alkyl group of Cι2-Cιs and M is a cation including sodium, magnesium, ammonium, and substituted ammonium; alkylsulfate, RSO M wherein R is an alkyl group of C12-C20 and M is a cation including sodium, magnesium, ammonium, and substituted ammonium; or alkylether sulfate, REnSO4M wherein R is an alkyl group of Cι2-C2n, E is ethylene oxide, CH2CH2O, n is an integer of 0 to 5, and M is a cation including sodium, magnesium, ammonium, and substituted ammonium.
4. The liquid detergent composition according to claim 1 , wherein the aryl boronic acid is that as represented by Formula I:
Figure imgf000028_0001
X Y , wherein, X and Y are independently hydrogen, Cι~C6 alkyl, aryl, substituted C1-C-6 alkyl, substituted aryl, hydroxyl, hydroxyl derivative, amine, Cι-C6 alkylated amine, amine derivative, halogen, nitro, thiol, thiol derivative, aldehyde, acid and its salt, ester, sulfonate, or phosphonate.
5. The liquid detergent composition according to claim 4, wherein the aryl boronic acid is 3-nitrophenyl boronic acid, phenyl boronic acid, or 3,5-dichlorophenyl boronic acid.
6. The liquid detergent composition according to claim 1 , wherein the protease is subtilisin protease, an extraceliuar alkaline protease from aikalophilic Vibrio metschnikovii strain RH530 under deposition number KCTC 0088BP, alcalase™, esperase™, savinase™, maxatase™, maxacal™, or maxapem™, which is protein engineered Maxacal.
7. The liquid detergent composition according to claim 1 , wherein the liquid detergent composition has pH of 8.5 to 11.0.
8. The liquid detergent composition according to claim 1 , further comprising a second detergent-compatible enzyme selected from the group consisting of amylase, lipase, cellulase, oxidoreductase, and a mixture thereof; an enzyme stabilizer selected from the group consisting of propylene glycol, ethylene glycol, and polyoxyethylene glycol; an enzyme solubilizer selected from the group consisting of ethanol, ethylene glycol, propylene glycol, sodium cumene sulfonate, sodium xylene sulfonate, and urea; and a builder selected from the group consisting of sodium carbonate, sodium hydroxide, potassium hydroxide, triethanolamine, diethanolamine, and monoethanolamine.
PCT/KR2003/001434 2002-07-20 2003-07-19 Alkaline liquid detergent composition WO2004009752A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003247189A AU2003247189A1 (en) 2002-07-20 2003-07-19 Alkaline liquid detergent composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2002-0042756 2002-07-20
KR1020020042756A KR20040008986A (en) 2002-07-20 2002-07-20 Akaline liquid detergent compositions

Publications (1)

Publication Number Publication Date
WO2004009752A1 true WO2004009752A1 (en) 2004-01-29

Family

ID=30768146

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2003/001434 WO2004009752A1 (en) 2002-07-20 2003-07-19 Alkaline liquid detergent composition

Country Status (3)

Country Link
KR (1) KR20040008986A (en)
AU (1) AU2003247189A1 (en)
WO (1) WO2004009752A1 (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007025549A1 (en) * 2005-09-02 2007-03-08 Novozymes A/S Stabilization of concentrated liquid enzyme additives
WO2008116915A1 (en) 2007-03-27 2008-10-02 Novozymes A/S Stable enzyme solutions and method of manufacturing
CN101899364B (en) * 2009-05-14 2011-07-20 浙江绿朋环保科技有限公司 Plant environment-friendly cleaning agent
DE102010030609A1 (en) * 2010-06-28 2011-12-29 Henkel Ag & Co. Kgaa New proteases and agents containing them
WO2012065839A1 (en) * 2010-11-15 2012-05-24 Henkel Ag & Co. Kgaa Stabilized, liquid, enzyme-containing surfactant preparation
CN103183820A (en) * 2011-12-29 2013-07-03 辽宁奥克化学股份有限公司 Preparation method of polyoxyethylene/propylene ether with low polyethylene/propylene glycol content
CN104031755A (en) * 2014-06-12 2014-09-10 王希贵 Oil stain cleaning agent and preparation method thereof
JP2014523474A (en) * 2011-07-25 2014-09-11 ザ プロクター アンド ギャンブル カンパニー Detergent composition
AU2010299953B2 (en) * 2009-09-25 2015-02-12 Novozymes A/S Detergent composition
CN104711136A (en) * 2015-03-27 2015-06-17 上海景禧衣洁坊洗涤有限公司 Low-temperature pre-washing agent special for washing machine and preparation method thereof
WO2017144623A1 (en) * 2016-02-24 2017-08-31 Henkel Ag & Co. Kgaa Stabilization of protease in cleaning agents containing alkylbenzene sulphonate
EP2726590B1 (en) 2011-07-01 2017-10-18 Novozymes A/S Liquid detergent composition
CN110713866A (en) * 2018-07-13 2020-01-21 花王株式会社 Liquid detergent composition for clothing
EP3013931B1 (en) 2013-06-25 2020-02-12 Unilever N.V. Composition comprising glutamic-n,n-diacetate (glda), water and enzyme
CN111479912A (en) * 2017-11-30 2020-07-31 荷兰联合利华有限公司 Detergent composition comprising protease
EP3271448B1 (en) 2015-03-18 2021-09-08 Evonik Operations GmbH Composition comprising peptidase and biosurfactant
CN115537821A (en) * 2022-09-01 2022-12-30 深圳市豪龙新材料技术有限公司 Bio-enzyme detergent for metal surface and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4842769A (en) * 1985-07-26 1989-06-27 Colgate-Palmolive Co. Stabilized fabric softening built detergent composition containing enzymes
WO1992019707A1 (en) * 1991-04-30 1992-11-12 The Procter & Gamble Company Liquid detergents with an aryl boronic acid
WO1996041859A1 (en) * 1995-06-13 1996-12-27 Novo Nordisk A/S 4-substituted-phenyl-boronic acids as enzyme stabilizers

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5691292A (en) * 1992-04-13 1997-11-25 The Procter & Gamble Company Thixotropic liquid automatic dishwashing composition with enzyme
DE69415972T2 (en) * 1993-04-27 1999-08-12 Procter & Gamble LIQUID OR GRANULAR MACHINE DISHWASHER
KR100345997B1 (en) * 2000-07-05 2002-07-24 제일제당주식회사 Alkalic liquid detergent composition containing magnesium alkylbenzene sulfonate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4842769A (en) * 1985-07-26 1989-06-27 Colgate-Palmolive Co. Stabilized fabric softening built detergent composition containing enzymes
WO1992019707A1 (en) * 1991-04-30 1992-11-12 The Procter & Gamble Company Liquid detergents with an aryl boronic acid
US5472628A (en) * 1991-04-30 1995-12-05 The Procter & Gamble Company Liquid detergents with an aryl acid for inhibition of proteolytic enzyme
WO1996041859A1 (en) * 1995-06-13 1996-12-27 Novo Nordisk A/S 4-substituted-phenyl-boronic acids as enzyme stabilizers

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007025549A1 (en) * 2005-09-02 2007-03-08 Novozymes A/S Stabilization of concentrated liquid enzyme additives
JP2013116122A (en) * 2005-09-02 2013-06-13 Novozyme As Stabilization of concentrated liquid enzyme additive
WO2008116915A1 (en) 2007-03-27 2008-10-02 Novozymes A/S Stable enzyme solutions and method of manufacturing
US10590368B2 (en) 2007-03-27 2020-03-17 Novozymes A/S Stable enzyme solutions and method of manufacturing
US11827866B2 (en) 2007-03-27 2023-11-28 Novozymes A/S Stable enzyme solutions and method of manufacturing
JP2015042747A (en) * 2007-03-27 2015-03-05 ノボザイムス アクティーゼルスカブ Stable enzyme solution and production method
CN101646760B (en) * 2007-03-27 2014-11-26 诺维信公司 Stable enzyme solutions and method of manufacturing
CN101899364B (en) * 2009-05-14 2011-07-20 浙江绿朋环保科技有限公司 Plant environment-friendly cleaning agent
AU2010299953B2 (en) * 2009-09-25 2015-02-12 Novozymes A/S Detergent composition
DE102010030609A1 (en) * 2010-06-28 2011-12-29 Henkel Ag & Co. Kgaa New proteases and agents containing them
WO2012065839A1 (en) * 2010-11-15 2012-05-24 Henkel Ag & Co. Kgaa Stabilized, liquid, enzyme-containing surfactant preparation
EP2640818B1 (en) 2010-11-15 2018-04-25 Henkel AG & Co. KGaA Stabilized liquid surfactant composition comprising enzym
EP2726590B1 (en) 2011-07-01 2017-10-18 Novozymes A/S Liquid detergent composition
JP2014523474A (en) * 2011-07-25 2014-09-11 ザ プロクター アンド ギャンブル カンパニー Detergent composition
CN103183820A (en) * 2011-12-29 2013-07-03 辽宁奥克化学股份有限公司 Preparation method of polyoxyethylene/propylene ether with low polyethylene/propylene glycol content
CN103183820B (en) * 2011-12-29 2015-09-02 辽宁奥克化学股份有限公司 A kind of method preparing the polyoxy second/propylene ether of oligomeric second/content of propylene glycol
EP3013931B1 (en) 2013-06-25 2020-02-12 Unilever N.V. Composition comprising glutamic-n,n-diacetate (glda), water and enzyme
CN104031755A (en) * 2014-06-12 2014-09-10 王希贵 Oil stain cleaning agent and preparation method thereof
EP3271448B1 (en) 2015-03-18 2021-09-08 Evonik Operations GmbH Composition comprising peptidase and biosurfactant
CN104711136A (en) * 2015-03-27 2015-06-17 上海景禧衣洁坊洗涤有限公司 Low-temperature pre-washing agent special for washing machine and preparation method thereof
WO2017144623A1 (en) * 2016-02-24 2017-08-31 Henkel Ag & Co. Kgaa Stabilization of protease in cleaning agents containing alkylbenzene sulphonate
CN111479912A (en) * 2017-11-30 2020-07-31 荷兰联合利华有限公司 Detergent composition comprising protease
CN111479912B (en) * 2017-11-30 2021-08-10 联合利华知识产权控股有限公司 Detergent composition comprising protease
CN110713866A (en) * 2018-07-13 2020-01-21 花王株式会社 Liquid detergent composition for clothing
CN115537821A (en) * 2022-09-01 2022-12-30 深圳市豪龙新材料技术有限公司 Bio-enzyme detergent for metal surface and preparation method thereof
CN115537821B (en) * 2022-09-01 2023-10-27 深圳市豪龙新材料技术有限公司 Biological enzyme detergent for metal surface and preparation method thereof

Also Published As

Publication number Publication date
AU2003247189A1 (en) 2004-02-09
KR20040008986A (en) 2004-01-31

Similar Documents

Publication Publication Date Title
WO2004009752A1 (en) Alkaline liquid detergent composition
KR910006071B1 (en) Stable liquid detergent compositions
EP0832174B1 (en) 4-substituted-phenyl-boronic acids as enzyme stabilizers
EP0544777B1 (en) Enzymatic detergent composition and method for enzyme stabilization
EP0793709B1 (en) Naphthalene boronic acids
US20100210502A1 (en) Polycyclic Compounds as Enzyme Stabilizers
USH1776H (en) Enzyme-containing heavy duty liquid detergent
US5156773A (en) Stabilized enzymatic liquid detergent composition
AU733041B2 (en) Enzymes for recreational water
FI118341B (en) Enzyme stabilization by block copolymers
EP2383330A1 (en) A stabilized liquid enzyme composition
US5156761A (en) Method of stabilizing an enzymatic liquid detergent composition
EP0352244A2 (en) Stabilized enzymatic liquid detergent
JPH02227500A (en) Enzymatic liquid detergent composition
US5527487A (en) Enzymatic detergent composition and method for enzyme stabilization
CN1242035C (en) Detergent for washing infantile clothes
KR100420467B1 (en) a alkaline composition of liquid type cleanser containing nonionic surfactant
US6121225A (en) Stable aqueous enzyme compositions
JP2002294284A (en) Liquid detergent composition for clothes
KR100345997B1 (en) Alkalic liquid detergent composition containing magnesium alkylbenzene sulfonate
JPH0631427B2 (en) Enzyme-containing liquid detergent composition
JP2020084141A (en) Liquid detergent composition for fiber product
JPH08157872A (en) Enzyme-containing liquid detergent composition
JPH09279181A (en) Liquid cleaning composition
US20110230383A1 (en) Laundry Pretreatment Compositions Containing Fatty Alcohols

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP