HUP0600532A2 - Transparent/translucent liquid enzyme compositions in clear bottles comprising antioxidants - Google Patents

Description

It is expensive and must be added to the hot molten material, therefore there is a risk of operator burns.

International Publication No. 97/26315 (Colgate) discloses transparent containers with specific color values characterized by x and y values. Specific colorants are used in the liquid to match the container. This document does not disclose transparent liquids containing a mixture of specific combinations of antioxidants and enzyme capsules according to the invention.

British Patent No. 1303810 discloses a transparent liquid medium in which components distinguishable to the naked eye are suspended. However, detergent compositions containing antioxidants and enzyme capsules are not disclosed.

U.S. Patent No. 3,812,042 (Verdier) describes transparent packages containing liquids with a viscosity and transparency control system comprising urea, a short chain aliphatic alcohol and optionally a hydrotrope.

Surprisingly, it has been found that when a relatively small amount of antioxidant is added to a liquid containing enzymes, the loss of enzyme activity due to UV light is dramatically reduced. This unexpected effect was surprising due to the low concentration of the additive and the dispersion of the liquid in the matrix. The use of antioxidants has the advantage of being safer, as it can be added at a lower temperature than the temperature of the molten bottle base. The invention therefore relates to a transparent or translucent, high-performance liquid composition bottled in a transparent container, which comprises:

a) between 10 and 85% by weight of a surfactant, which may be anionic, nonionic, cationic, amphoteric or zwitterionic or a mixture thereof;

b) between 0.001 and 5% by weight of an enzyme, which may be a protease, lipase, cellulase, oxidase, amylase or a mixture thereof; and

c) between 0.001 and 3% by weight of an antioxidant;

wherein the composition has a light transmittance of at least 50% at a wavelength of about 410-800 nm in a 1 cm cuvette; and the bottle has a light transmittance of at least 25% at a wavelength of about 410-800 nm.

The invention therefore relates - in more detail - to transparent or clear liquids containing enzymes in transparent bottles, which contain an antioxidant that prevents the reduction of enzyme activity (e.g. caused by light passing through the transparent bottle, which damages the enzyme).

Antioxidants

Tocopherols, thiodipropionates, hydroquinones, diphenylamines, hindered phenols or cresols are preferably used as antioxidants. The above list of compound families is not limiting.

Particularly useful antioxidants for use in the present invention include metal chelating agents, ascorbic acid, mono- or polyhydrophenols, such as tocopherols, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), tert-butylhydroquinone (TBHQ), propyl gallate (PG), 2,4,5-trihydroxybutylphenone (THBP) or 4hydroxymethyl-2,6-di-tert-butylphenol. A particularly preferred antioxidant is ascorbic acid, BHA, BHT or a mixture thereof. Although not theoretically proven, antioxidants slow down the oxidation reaction by inhibiting the formation of free radicals in the initiation steps. This generally inhibits a chain reaction based on free radical transfer, since antioxidants act as hydrogen donors or free radical acceptors.

Other useful antioxidants are described in McCutcheon's Functional Materials, Volume 2, published by Manufacturing Confectioner Publishing Company (North American Edition, 1997).

Antioxidants can be used in amounts of between 0.001 and 3% by weight, preferably between 0.005 and 2% by weight, more preferably between 0.01 and 1% by weight.

Detergent preparations

Active ingredients

The compositions of the invention comprise one or more surface-active substances (surfactants), such surfactants being, for example, anionic, nonionic, cationic, ampholytic, zwitterionic surfactants or mixtures thereof. Preferred surfactant detergents for use in the invention are mixtures of anionic and nonionic surfactants, although it is understood that a surfactant may be used alone or in combination with any other surfactant or surfactants. The composition should contain at least 10% by weight, for example, 11 to 85%, preferably 15 to 70%, more preferably 16 to 65%; more preferably 20 to 65% by weight of the total weight of the composition.

Non-ionic surfactants

Nonionic synthetic organic detergents which can be used in accordance with the invention, either alone or in combination with other surfactants, are described below.

It is known that nonionic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group, and are typically prepared by the condensation of an organic aliphatic or alkylaromatic hydrophobic compound with ethyl oxide (which is hydrophilic in nature). Typical suitable nonionic surfactants are described in U.S. Patents 4,316,812 and 3,630,929.

In general, nonionic detergents are polyalkoxylated lipophilic compounds, where the desired hydrophilic-lipophilic balance is achieved by the addition of a hydrophilic poly(lower alkoxy) group and a lipophilic moiety. A preferred group of nonionic detergents are alkoxylated alkanols, where the alkanol contains 9-18 carbon atoms and the number of moles of alkylene oxide (2 or 3 carbon atoms) can be between 3 and 12. Among such materials, compounds which contain a fatty alcohol of 9-11 or 12-15 carbon atoms as the alkanol and also contain 8 or 5 to 9 alkoxy groups per mole are preferred.

Examples of such compounds include those containing a C12-15 alkanol and about 7 ethylene oxide groups per mole, such as Neodol™ 25-7 or Nedolol™ 23-6.5 (manufactured by Shell Chemical Company, Inc.). The former is a condensation product of long-chain fatty alcohols having an average of about C12-15 atoms and about 7 moles of ethylene oxide, the latter is a mixture of a C12-13 long-chain fatty alcohol and ethylene oxide, where the number of ethylene oxide groups present is about 6.5. The long-chain alcohols may be primary alkanols.

Other useful nonionic detergents include those sold commercially under the well-known trade name Plurafac. Plurafac products are the reaction products of longer, straight chain alcohols with a mixture of ethylene and propylene oxides, and contain mixed chain ethylene oxide and propylene oxide terminated with a hydroxyl group. For example, a fatty alcohol having 13-15 carbon atoms with 6 moles of ethylene oxide and 3 moles of propylene oxide; a fatty alcohol having 13-15 carbon atoms with 7 moles of ethylene oxide and 4 moles of propylene oxide; or a fatty alcohol having 13-15 carbon atoms with 10 moles of ethylene oxide and 5 moles of propylene oxide, or any mixture thereof.

Another family of liquid nonionic detergents are those manufactured by Shell Chemical Company, Inc. under the brand name Dobanol. Examples include Dobanol 91-5 (an average of 5 moles of ethylene oxide-ethoxylated fatty alcohols of 9-11 carbon atoms) or Dobanol 23-7 (an average of 7 moles of ethylene oxide-ethoxylated fatty alcohols of 12-15 carbon atoms per mole of fatty alcohol).

Preferred nonionic surfactants in the compositions of the invention are primary fatty alcohols of 12-15 carbon atoms with a relatively low ethylene oxide content of between 7 and 9 moles, and fatty alcohols of 9-11 carbon atoms ethoxylated with about 5-6 moles of ethylene oxide.

Another class of nonionic surfactants that can be used in the composition of the invention are glycoside surfactants. Glycoside surfactants that can be used in the composition of the invention include:

Compounds of the general formula RO-R'Oy(Z) _x , where in the formula R is a monovalent organic radical having 6-30 (preferably 8-18) carbon atoms; R' is a divalent hydrocarbon radical having 2-4 carbon atoms; O is an oxygen atom; y is a number having an average value between 0 and 12, but preferably zero; Z is a residue derived from a reducing sugar having 5 or 6 carbon atoms; and x is a number having an average value between 1 and 10 (preferably 1.5 and 10).

A particularly preferred glycoside surfactant group in the application of the invention is formed by compounds of the above general formula, where in the formula R is a monovalent organic radical (straight or branched chain) having 6-18 (preferably 8-18) carbon atoms; y is zero; Z is glucose or a residue derived therefrom; and x is a number whose average value is between 1 and 4 (preferably 1 and 4).

Nonionic surfactants particularly useful in the present invention include, but are not limited to, alcohol ethoxylates (e.g., Neodol 25-9, manufactured by Shell Chemical Co.), alkyl phenol ethoxylates (e.g., Tergitol NP-9, manufactured by Union Carbide Corp.), alkyl polyglucosides (e.g., Glicapon™ 600CS, manufactured by Henkel Corp.), polyoxyethyleneated polyoxypropylene glycols (e.g., Pluronic™ L-65, manufactured by BASF Corp.), sorbitol esters (e.g., Emsorb™ 2515, manufactured by Henkel Corp.), polyoxyethyleneated sorbitol esters (e.g., Emsorb™ 6900, manufactured by Henkel Corp.), alkanolamides (e.g., Alkamid™ DC212/SE, manufactured by Rhone-Poulenc Co.), or N-alkylpyrrolidones (e.g., Surfadon™ LP-100, manufactured by ISP Technologies Inc.).

The nonionic surfactants are used in an amount of between 0 and 70%, preferably between 5 and 50%, more preferably between 10 and 40%, based on the total weight of the composition.

Mixtures of two or more nonionic surfactants may also be used.

Anionic surfactant detergents

For the purposes of the invention, anionic surfactants are surface-active compounds which contain in their molecular structure a long-chain, hydrophobic hydrocarbon group and a hydrophilic group, i.e. a water-solubilizable group, such as a sulfonate or sulfate group. Anionic surfactants may be, for example, alkali metal salts (such as sodium or potassium salts) of water-soluble longer-chain alkylbenzene sulfonates, alkyl sulfonates, alkyl sulfates or alkyl polyether sulfates. They may also be fatty acids or saponified fatty acids. Preferred anionic surfactants are alkali metal, ammonium or alkanolamide salts of longer-chain alkylbenzene sulfonates or alkali metal, ammonium or alkanolamide salts of longer-chain alkylsulfonates. Preferred longer chain alkyl sulfonates are sulfonates containing alkyl groups of 8 to 26, preferably 12 to 22, more preferably 14 to 18 carbon atoms. In the alkyl benzene sulfonate, the alkyl group preferably contains 8 to 16, more preferably 10 to 15 carbon atoms. A particularly preferred alkyl benzene sulfonate is the sodium or potassium salt of dodecyl benzene sulfonate, such as sodium (straight-chain dodecyl) benzene sulfonate. Primary and secondary alkyl sulfonates can be prepared by reacting long chain alpha-olefins with sulfites or hydrogen sulfites, such as sodium hydrogen sulfite. Alkyl sulfonates can also be prepared by reacting long chain normal paraffin hydrocarbons with sulfur dioxide and oxygen. This process is described in U.S. Patents 2,503,280, 2,507,088, 3,372,188 and 3,260,741, and provides normal or secondary long chain alkyl sulfonates suitable for use as surfactant detergents.

The alkyl substituent is preferably a straight chain, e.g. a normal alkyl group, but branched chain alkyl sulfonates can also be used, although they are not as biodegradable. The alkane, i.e. alkyl substituent may be terminally sulfonated or may be linked, for example, via one carbon atom of the chain to another group containing a secondary sulfonate group. It will be apparent to the skilled person that the substituent may be linked to any carbon atom of the alkyl chain. Longer chain alkyl sulfonates may be used as alkali metal, e.g. sodium or potassium salts. Preferred salts are sodium salts. Preferred alkyl sulfonates are primary normal alkyl sodium or potassium sulfonates having 10-18 carbon atoms, with the primary normal alkyl sulfonate salt having 10-15 carbon atoms being more preferred.

Long-chain alkylbenzene sulfonates and mixtures of long-chain alkylsulfonates and long-chain alkylbenzene sulfonates and alkyl polyether sulfates can be used in the practice of the invention.

The alkali metal salts of alkylbenzenesulfonates can be used in an amount of between 0 and 70%, preferably between 10 and 50% and more preferably between 10 and 20%, based on the total weight of the product.

The alkali metal sulfonate salts can be used in admixture with alkylbenzene sulfonates, where their amount may be between 0 and 70%, preferably between 10 and 50%, based on the total weight of the product.

Normal alkyl and branched alkyl sulfates (e.g. primary alkyl sulfates) can also be used as anionic components.

The long chain alkyl polyether sulfates used in the present invention may be normal or branched chain alkyl groups and contain alkoxy groups of two or three carbon atoms. Normal long chain alkyl polyether sulfates are preferred because they have a higher degree of biodegradability compared to branched chain alkyl derivatives, and the short chain polyalkoxy groups are preferably ethoxy groups.

Preferred long-chain alkyl polyethoxy sulfates according to the invention are those

Compounds of the general formula R'-O( _CH2CH2O )p-SO3M, where R' is an alkyl group having 8-20 carbon atoms, preferably 10-18 carbon atoms, more preferably 12-15 carbon atoms; p is between 2 and 8, preferably between 2 and 6, more preferably between 2 and 4; M is an alkali metal cation, for example sodium or potassium, or ammonium.

Sodium and potassium salts are preferred.

A preferred long chain polyethoxylated alkyl sulfate is

Sodium salt of triethoxy-(C12-C15 alcohol) sulfate with the formula _C12 -i5-O-(CH2CH2O) ₃ -SO3Na.

Examples of alkyl ethoxy sulfates useful in the present invention include the sodium salt of C12-15 normal or primary alkyl triethoxy sulfate; the sodium salt of n-decyl diethoxy sulfate; the ammonium salt of C12 primary alkyl diethoxy sulfate; the sodium salt of C12 primary alkyl triethoxy sulfate; the sodium salt of C15 primary alkyl tetraethoxy sulfate; the sodium salt of mixed C14-15 normal primary alkyl mixed and tetraethoxy sulfate; the sodium salt of stearyl pentaethoxy sulfate; and the potassium salt of mixed C10-18 normal primary alkyl triethoxy sulfate.

Normal alkyl ethoxy sulfates are rapidly biodegradable and are advantageous to use. Alkyl poly(short chain alkoxy) sulfates can be used in admixture with each other and/or in admixture with the above-mentioned long chain alkyl benzenes, alkyl sulfonates or alkyl sulfates.

The alkali metal salt of the long chain alkyl polyethoxy sulfate may be used together with alkylbenzene sulfonate and/or an alkyl sulfonate or sulfonate, and in an amount of between 0 and 70%, preferably between 10 and 50%, more preferably between 10 and 20%, based on the total weight of the composition.

Particularly useful anionic surfactants in the present invention include, but are not limited to, straight chain alkylbenzene sulfonates (e.g., Vista™ C-500, manufactured by Vista Chemical Co.), alkyl sulfates (e.g., Polystep™ B-5, manufactured by Stepan Co.), polyoxyethyleneated alkyl sulfates (e.g., Standapol™ ES-3, manufactured by Stepan Co.), alpha-olefin sulfonates (e.g., Witconate™ AOS, manufactured by Witco Corp.), alpha-sulfomethyl esters (e.g., Alpha-Step™ MC-48, manufactured by Stepan Co.), or isethionates (e.g., Jordapon™ Cl, manufactured by PPG).

Industries Inc.).

The anionic surfactants are used in an amount of between 0 and 60%, preferably between 5 and 40%, more preferably between 8 and 25%, based on the total weight of the composition.

Cationic surfactants

A number of cationic surfactants are known in the art, and almost all cationic surfactants containing at least a long chain alkyl group of from 10 to 24 carbon atoms can be used in the composition of the invention. Such compounds are described in "Cationic Surfactants", Jungermann, 1970, which is incorporated herein by reference.

The surfactants of the invention include specific cationic surfactants described in U.S. Patent No. 4,497,718.

As with nonionic and anionic surfactants, cationic surfactants may be used alone or in combination with any other surfactant known in the art in the compositions of the invention. Of course, the compositions may also contain no cationic surfactants at all.

Amphoteric surfactants

Ampholytic synthetic detergents are generally aliphatic derivatives of heterocyclic secondary or tertiary amines, where the aliphatic group may be straight or branched chain, and in which one of the aliphatic substituents contains between 8 and 18 carbon atoms, and at least one substituent contains an anionic water-solubilizable group, such as carboxyl, sulfonate, sulfate groups. Such compounds include, for example, sodium 3-(dodecylamino)propionate, sodium 3-(dodecylamino)propane-1-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadecanoate, disodium 3-(N-carboxymethyldodecylamino)propane-1-sulfonate, disodium octadecyl iminodiacetate, sodium 1-carboxymethyl-2undecylimidomidazole or sodium N,N-bis(2-hydroxyethyl)-2-sulfo-3 dodecoxypropylamine. Sodium 3-(dodecylamino)propane-1-sulfonate is preferred for use in the invention.

Zwitterionic surfactants are generally derivatives of secondary or tertiary amines, derivatives of secondary or tertiary heterocyclic amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. The cationic atom of the quaternary compound may be part of a heterocyclic ring. All of the above-mentioned compounds contain at least one straight or branched aliphatic group having 3 to 18 carbon atoms, and at least one aliphatic substituent containing an anionic water-solubilizing group, such as a carboxysulfonate, sulfate, phosphate, or phosphonate group.

Specific examples of zwitterionic surfactants can be found in U.S. Patent No. 4,062,647.

The amount of amphoteric substance used may vary between 0 and 50%, preferably between 1 and 30%, based on the total amount of the composition.

It should be noted that the compositions of the invention are preferably isotropic (meaning that the composition is macroscopically homogeneous in phase) and transparent or translucent.

The amount of surfactant used should be at least 10%, preferably at least 15%, more preferably at least 20% by weight of the total amount of the composition.

Frame materials/electrolyte

Builders useful in the present invention may be conventional organic or inorganic alkaline detergent builders, which may be used in amounts of between 0 and 50%, preferably between 3 and 35%, based on the total weight of the composition.

The term electrolyte as used herein refers to any water-soluble salt.

Preferably, the composition comprises at least 1%, more preferably 5% and most preferably 10% by weight of electrolyte, based on the total amount of the composition. The electrolyte may be a detergent builder, such as an inorganic sodium tripolyphosphate builder, or a non-functional electrolyte, such as sodium sulfate or sodium chloride. Preferably, the inorganic builder comprises part or all of the electrolyte.

The composition contains at least 1%, preferably at least 3%, more preferably between 3 and 50% by weight of electrolyte, based on the total amount of the composition.

The compositions of the invention are capable of suspending particulate solids, although systems in which such solids are in suspension are particularly preferred. The solids are undissolved electrolytes, the same as or different from the saturated electrolyte in solution. Additionally, or alternatively, they may be materials that are substantially insoluble in water. Such substantially insoluble materials include, for example, aluminosilicate framework materials or calcite abrasives.

Suitable inorganic alkaline detergent builders include, for example, water-soluble alkali metal phosphates, polyphosphates, borates, silicates or carbonates. More particularly, suitable salts include sodium and potassium triphosphates, pyrophosphates, orthophosphates, hexametaphosphates, tetraborates, silicates and carbonates.

Suitable organic alkaline detergent builder salts include (1) water-soluble amino polycarboxylates, such as sodium or potassium ethylenediamine tetraacetates, nitrilotriacetates or N-(2-hydroxyethyl) nitrilodiacetates; (2) water-soluble salts of phytic acid, such as sodium or potassium phytates (see U.S. Patent No. 2,379,942); (3) water-soluble polyphosphonates, including in particular the sodium, potassium and lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid; the sodium, potassium and lithium salts of methylenediphosphonic acid; the sodium, potassium and lithium salts of ethylenediphosphonic acid; the sodium, potassium and lithium salts of ethane-1,1,2-triphosphonic acid. Other examples include alkali metal salts of ethane-2-carboxy-1,1-diphosphonic acid, hydroxymethanediphosphonic acid, carboxyldiphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3tetraphosphonic acid and propane-1,2,2,3-tetraphosphonic acid; (4) water-soluble salts of polycarboxylated polymers and copolymers as described in U.S. Patent No. 3,308,067.

Furthermore, polycarboxylated scaffolds, including water-soluble salts of mellitic acid, citric acid and carboxymethyloxysuccinic acid, salts of polymers of itaconic acid and maleic acid, tartrate monosuccinate, tartrate disuccinate and mixtures thereof (TMS/TPS), are also suitably employed.

Certain zeolites and aluminosilicates may also be used. Such aluminosilicate which may be used in the composition of the invention is an amorphous, water-insoluble, hydrated compound of the formula Na _x [(AIO2) _y .SiO2], where x is a number between 1.0 and 1.2 and y is 1, and which is characterized by an ion exchange capacity of 50 mg eq. CaCOs/g Mg++ and a particle diameter of between 0.01 and 5 mm. Such ion exchange frameworks are described in more detail in British Patent Specification No. 1470250.

Another water-insoluble synthetic aluminosilicate ion exchange material which can be used in the composition according to the invention is a compound of the general formula Na2[(AIO2)y(SiO ₂ )]xH ₂ O, which is crystalline in nature, wherein z and y are independently integers of at least 6; the molar ratio between z and y is between 1.0 and 0.5, and x is an integer of 15 and 264; the particle size of the above aluminosilicate ion exchange material is between 0.1 mm and 100 mm; it has a calcium ion exchange capacity of 200 mg equivalent CaCCh hardness when tested on an anhydrous basis, and a calcium ion exchange capacity of at least 0.0288 g/l/min/g on an anhydrous basis. Such ion exchange frameworks are described in more detail in British Patent Specification No. 1429143.

Enzymes

The enzymes that can be used in the composition according to the invention are described in more detail below.

If a lipase is used, the lipolytic enzyme is a fungal lipase produced by Humicola lanuginosa or Thermomyces lanuginosus or

It may be a bacterial lipase that shows a positive immunological cross-reaction with the lipase antibody produced by the microorganism Chromobacter viscosum var. lipolyticum NRRL B-3673. This microorganism is described in Dutch Patent No. 154269 (Toyo Jozo Kabushiki Kaisha) and is deposited in the permanent collection of the Fermentation Research Institute, Agency of Industrial Science and Industry, Tokyo, Japan, under the number KO Hatsu Ken Kin Ki 137, and is also available to the public under the number NRRL b-3673 at the United States Department of Agriculture, Agricultural Research Service, Northern Utilization and Development Division at Peoria, Illinois, USA. The lipase produced by the microorganism - hereinafter referred to as "TJ lipase" - is commercially available from Toyo Jozo Co., Tagata, Japan. These bacterial lipases are detected by the standard and well-known immunodiffusion method of Ouchterlony [Acta. Med. Scan., 133, 76-79 (1930)] must show a positive immunological cross-reaction with the TJ lipase antibody.

The antiserum is prepared as follows:

Equal volumes of 0.1 mg/ml antigen and Freund's adjuvant (complete or incomplete) are mixed until an emulsion is formed. A 2 ml emulsion sample is injected into two female rabbits according to the following scheme:

Day 0: antigen in complete Freund's adjuvant;

Day 4: antigen in complete Freund's adjuvant;

Day 32: antigen in incomplete Freund's adjuvant;

Day 64: booster in incomplete Freund's adjuvant.

Serum containing the desired antibody is prepared by centrifuging coagulated blood collected on day 67.

The titer of anti-TJ-lipase antiserum is determined by observing the precipitates of serial dilutions of antigen and antiserum solutions according to the Ouchterlony method. The antiserum is diluted so that precipitation can still be observed at an antigen concentration of 0.1 mg/ml.

In the practice of the invention, any bacterial lipase that exhibits the above positive immunological cross-reaction with the TJ-lipase antibody can be used. Such lipases are typically, for example, lipase from Pseudomonas fluorescens IAM 1057 (produced under the trade name Amano-P lipase by Amano Pharmaceutical Co., Nagoya, Japan), lipase from Pseudomonas fragi FERM P 1339 (sold under the trade name Amano B), lipase from Pseudomonas nitroreducens var. lipolyticum FERM 1338, lipase from Pseudomonas species (sold under the trade name Amano CES), lipase from Pseudomonas cepacia, lipases from Chromobacter viscosum, such as lipase from Chromobacter viscosum var. lipolyticum NRRL B-3673, which is commercially available from Toyo Jozo Co., Tagata, Japan; and U.S. Biochemical Corp. Chromobacter viscosum lipases produced by the companies USA and Diosynth Co., Netherlands, or lipases from Pseudomonas gladioli.

As the above fungal lipase, for example, lipase derived from Humicola lanuginosa (manufactured by Amano, sold under the trade name Amano CE); lipase derived from Humicola lanuginosa described in the aforementioned European Patent Specification No. 0258068 (NOVO); and lipase produced by cloning a gene extracted from Humicola lanuginosa and expressing it in Aspergillus oryzae (commercially marketed by NOVO industri A/S under the trade name "Lipolase"). A preferred lipase in the application of the invention is Lipolase.

While a number of specific lipase enzymes have been described above, it is readily apparent that any lipase may be used in the composition of the invention which imparts suitable lipolytic activity to the composition, and the specific selection of a lipase enzyme should not be construed to limit the scope of the invention.

In this embodiment of the invention, the lipases are used in the liquid detergent composition in an amount such that, when the composition is added in an amount of 0.1 to 10, more preferably 0.5 to 7, most preferably 1 to 2 g/l, during a wash cycle, its lipolytic activity is between 100 and 0.005.

LU/ml, preferably between 25 and 0.05 LU/ml.

A Lipase Unit (LU) is the amount of lipase that produces 1 mmol of titratable fatty acid per minute under the following conditions and pH: temperature 30°C; pH 9; the substrate is an emulsion containing 3.3% by weight of olive oil and 3.3% gum arabic, in the presence of 13 mmol/l Ca ²⁺ and 20 mmol/l NaCl in 5 mmol/l Tris buffer.

Of course, mixtures of the above lipases can also be used. The lipases can be used in an unpurified form or in a purified form, for example by well-known absorption methods, such as phenyl-sepharose absorption methods.

If a protease is used, the proteolytic enzyme may be of plant, animal or microorganism origin. It may preferably be of microorganism origin, such as fungus, yeast, mold or bacteria. Particularly preferred are bacterial subtilisin type proteases, which can be extracted from certain strains of B. subtilis or B. licheniformis. Proteases that can be used in the composition according to the invention may be, for example, Alcalase™, Savinase™, Esperase™ (manufacturer: NOVO Industri A/S); Maxatase™, Maxacal™ (manufacturer: Gist-Brocades); Kazusase™ (manufacturer: Showa Denko); BPN, BPN' proteases or the like. The amount of protease added to the composition may be between 0.05 and 50,000 GU/mg, preferably between 0.1 and 50 GU/mg, based on the final composition of the product. Of course, mixtures of different proteolytic enzymes may also be used.

While a number of specific lipase enzymes have been described above, it is readily apparent that any protease may be used in the composition of the invention which imparts suitable lipolytic activity to the composition, and the specific selection of a proteolytic enzyme should not be construed to limit the scope of the invention.

It is readily apparent that in addition to lipases and proteases, other enzymes such as cellulases, oxidases, amylases, peroxidases or other similar enzymes well known in the art may also be used in the composition of the invention. If necessary, the enzymes may be used together with cofactors that enhance enzyme activity, for example, if necessary, they may be used in enzyme systems. It is also readily apparent that enzymes that have been mutated at various positions (such as enzymes designed to increase efficiency and/or stability) are also within the scope of the invention. A commercially available engineered enzyme of this type is Durazym manufactured by Novo.

Additional ingredients

In addition to the above enzymes, several other additional ingredients can be used.

Buffers providing alkalinity, such as monoethanolamine, triethanolamine, borax, sodium silicate or the like, may be added to the composition of the invention.

Hydrotropic substances such as ethanol, sodium xylene sulfonate or sodium cumene sulfonate may be added to the composition of the invention.

Other materials, such as clays, especially water-insoluble clays, may be useful in the compositions of the invention. A particularly useful additive is bentonite. This latter material is primarily montmorillonite. Montmorillonite is known to be a hydrated aluminum silicate in which 1/6 of the aluminum atoms may be replaced by magnesium atoms which may be freely combined with varying amounts of hydrogen, sodium, potassium, calcium, etc. Bentonite useful as a detergent additive in its well-purified form (i.e. free from coarse or fine sand) contains at least 30% montmorillonite and thus has a cation exchange capacity of at least 50 to 75 meg per 100 g of bentonite. Particularly preferred bentonites are the Wyoming or Western U.S. bentonites, which are sold under the names Thixo-jels 1, 2, 3 and 4 by Georgia Kaolin Co. It is known from British Patent Specification No. 401413 (assigned to Marriott) and Patent Specification No. 461221 (assigned to Mariott and Guam) that these bentonites soften textiles.

Additional desirable functional properties in the detergent product of the invention

-:·· -::• · · · · «· ··· · or to provide properties of an aesthetic nature, a number of other detergent additives or performance enhancers may be added.

The physical stability and anti-settling properties of the composition of the invention can be improved by adding a small but effective amount of an aluminum salt of a longer chain fatty acid. Thus, an amount of aluminum stearate between 0 and 3%, preferably between 0.1 and 2% and more preferably between 0.5 and 1.5% can be added as a stabilizing agent.

The composition of the invention may also contain minor amounts of soil suspending or anti-redeposition agents, such as polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose. A preferred anti-redeposition agent is sodium carboxymethyl cellulose, which has a CM/MC ratio of 2:1 and is sold under the trade name Relatin DM 4050.

Other minor components may include soil release agents, such as anti-flocculation polymers. Typically, an anti-flocculation polymer consists of a hydrophilic backbone and one or more hydrophobic side chains. Anti-flocculation polymers useful in the composition of the present invention are described in more detail in U.S. Patent No. 5,147,576. When used, the anti-flocculation polymer will generally comprise between 0.1 and 5%, preferably between 0.1 and 2%, and most preferably between 0.5 and 1.5% of the composition.

Optical brighteners can also be used for wool, polyamide and polyester fabrics. As optical brighteners, Tinopal™, stilbene, triazole or benzidine sulfone preparations, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidine sulfone, etc., most preferably combinations of stilbene and triazole can be used. A preferred brightener is Stilbene Brightener N4, which is a dimorpholine dianilino stilbene sulfonate.

Antifoaming agents, such as silicone compounds such as Silicane L 7604, may also be added in small, effective amounts.

The composition of the invention may also contain bactericides, such as tetrachlorosalicylanilide or hexachlorophene; fungicides; dyes; (water-dispersible) pigments; preservatives, such as formalin; ultraviolet absorbers; anti-yellowing agents, such as sodium carboxymethylcellulose; pH modifiers and pH buffers; color-safe bleaching agents; perfumes; dyes and bluing agents, such as Iragon Blue L2D, Detergent Blue 472/372 or ultramarine blue. Soil release polymers and cationic softeners may also be used.

The above list of additional ingredients is not exclusive, and the preparation may also include any additional raw materials that may not be listed but are well known in the literature.

If desired, the composition of the invention may contain one or more of the following ingredients: zwitterionic surfactants (such as Miratain™ BET C-30, manufactured by Rhone-Poulenc Co.), cationic surfactants (such as Schercamox™ DML, manufactured by Scher Chemicals, Inc.), fluorescent dye, anti-redeposition polymers, anti-discoloration polymers, soil release polymers, protease enzymes, lipase enzymes, amylase enzymes, cellulase enzymes, peroxidase enzymes, enzyme stabilizers, fragrances, opacifiers, UV absorbers, scaffolds, and suspended particles with a particle size of 300-5000 microns.

The composition of the invention has a light transmittance of at least 50% in a 1 cm cuvette at a wavelength of approximately 410-800 nm, preferably at a wavelength of 570-690 nm - where the composition is essentially free of dyes.

Alternatively, the light transmittance of the preparation is measured in the visible light wavelength range (approximately 410-800 nm) and shows an absorbance value of up to 0.3, which corresponds to a transmittance of at least 50% when using the above wavelength range and cuvette.

Even with very low UV-B radiation transmission, the

Decreased enzyme activity as a result of UV damage.

Bottle material

Transparent bottle materials that can be used with the composition of the invention include, but are not limited to, polypropylene (PP), polyethylene (PE), polycarbonate (PC), polyamides (PA) and/or polyethylene terephthalate (PETE), polyvinyl chloride (PVC) or polystyrene (PS).

The transparent or translucent container according to the invention preferably has a light transmittance of at least 25%, more preferably at least 30%, even more preferably at least 40%, most preferably at least 50% in the visible spectrum of light (approximately 410-800 nm).

Alternatively, the bottle's absorbency can be measured and can be no more than 0.6 (corresponding to 25% permeability) or have a permeability of at least 25%, where % permeability = Qabsorbency X 100%

According to the objective of the invention, if the light transmission at a given wavelength in the visible light range is at least 25%, the container is classified as transparent/transparent or transparent.

Even with very low UV-B radiation transmission through the container wall, a decrease in enzyme activity as a result of UV damage can occur.

The bottle of the invention may be of any shape or size suitable for the storage and packaging of household liquids. For example, the container may be of any size, but generally has a maximum capacity of between 0.05 and 15 L, preferably between 0.1 and 5 L, more preferably between 0.2 and 2.5 L. Preferably, the container is easy to handle. For example, the container may have a handle or be provided with a portion that allows the container to be easily lifted or carried with one hand. The container should preferably have a means for pouring out the liquid detergent composition and a means for reclosing the container. The pouring means may be of any size or shape, but preferably is wide enough to allow easy dispensing of the liquid detergent composition. The closure means may be of any size or shape, but generally is a screw-on or snap-on device for closing the container. The closure means may be a cap removable from the container. Alternatively, the cap may be attached to the container, whether the container is closed or open. The closure means may also be incorporated into the bottle.

The following examples are intended to illustrate the invention and are not intended to be limiting in any way. All percentages herein, unless otherwise indicated, are by weight.

Methods

Measurement of absorptivity and light transmittance

Instrument: Milton Roy Spectronic 601

Proceedings:

1. Turn on the spectrophotometer and power supply box and allow to warm up for 30 minutes.

2. Set the wavelength

- enter the desired wavelength on the keyboard (for example 590, 640, etc.);

- press the [second function] button;

- press the “go to X”[yes] button;

- then the machine is ready to read at the selected wavelength.

3. Reset the device

- press the [second function] button;

- press the “zero A” [%/T/A/C] button;

- we can read the value "XXX NM 0.000 A T".

4. Open the cover and place the sample vertically against the sensor.

5. Close the lid and read the data (e.g. 640 NM 0.123 A T).

Note: All readings are taken in “A” mode (absorbance mode).

Note: the device must be zeroed each time the wavelength is changed and/or the sample is changed.

Absorbency values of two typical plastic bottles

Wavelength (nm) Polyethylene (HDPE); 0.960 mm thick Polypropylene (PP); 0.423 mm thick 254 (not visible) 1,612 1,886 310 (not visible) 1,201 0.919 360 (not visible) 0.980 0.441 590 (visible range) 0.525 0.190 640 (visible range) 0.477 0.169

Synthetic sunlight box (appliance to be used in the examples; only used in the UVA and UVB range)

Box dimensions and appearance:

Length: 1.22 m

Width: 0.61 m

Height: Made from 0.61 m mm glued board. The box is placed approximately 5.08 cm above the ground for air circulation. A small ventilation hole is provided in the coating of the box. Four lamps are placed on the longer side of the box, two on each side, approximately 15.24 cm apart.

The fan is installed to keep the internal temperature constant during the experiment, ensuring that any noticeable effects are due solely to ultraviolet radiation and not heat.

The samples are placed in open containers and placed in the box. The open containers are used to prevent the material of the container from interfering with the light rays. An open container of water is also placed in the box. This water maintains a constant humidity level and slows down the evaporation of the open samples. After a certain period of time, the samples are removed from the box, the evaporated water is checked, and the UV effects are also measured.

Accelerated atmospheric effect

According to the “Sunlight, UV and Accelerated Weathering Technical Bulletin LU-0822” and the QUV Accelerated Weathering Testers from Q-panel Leg Products, the literature references are:

Sunlight is a major damaging factor for plastics, fabrics, paints and other organic materials. Although UV light only makes up 5% of sunlight, it is responsible for the majority of photochemical damage. This is because photochemical efficiency increases with decreasing wavelength. It has long been recognized that short-wavelength ultraviolet radiation is responsible for the majority of damage caused. Accelerated weathering equipment is widely used in research and development, quality control and material qualification. These tests use a variety of light sources to simulate sunlight and damage caused by sunlight.

To model damage caused by sunlight, it is not necessary to provide the entire spectrum of sunlight. For most materials, modeling short-wavelength UV light is sufficient. For our specific purposes, we selected a UVA-340 lamp. The emission of this lamp is predominantly in the UV-A range, with only a small portion in the UV-B range. This lamp models sunlight well from 370 nm to the lower limit of sunlight at 295 nm.

Example 1

Samples of liquid detergents containing protease and lipase (as shown in Table 1 below) are placed in 2.54 cm diameter, sealed-top glass jars and exposed to UV radiation at 254 nm and 110 microwatts/ ^cm2 (5 days, 71 cm from the light source). After every 24 hours, the samples are weighed and opened to replace evaporated water. The enzyme activity of the UV-exposed samples is determined using appropriate substrates (e.g., casein as a protease substrate and p-nitrophenol valerate as a lipase substrate). The residual activity is expressed as a percentage of the original activity of the sample before UV irradiation. The samples contain 25 mmol/l ascorbic acid, 2.5 mmol/l BHA or 2.5 mmol/l BHT as preservatives. This corresponds to 0.044% by weight of ascorbic acid, 0.045% by weight of BHA and 0.05% by weight of BHT. The control sample does not contain such preservatives. The results are shown in Table 2a below.

Table 1

Detergent preparations

100% effective raw material Percentage by weight Neodol 25-9* 6-8 Alcohol ethoxy sulfate 12-15 Straight-chain alkylbenzene sulfonate 6-9 Sodium citrate dihydrate 3-6 Propylene glycol 4-8 Sorbitol 3-6 Sodium tetraborate pentahydrate 2-4 Smaller amounts of additives and water Up to 100%

*C12-C15 alkoxylated (9EO) chain group

Table 2a

Effect of antioxidants on enzyme stability when exposed to UV-C radiation (254nm)

Sample Enzyme After 24 hours, the remaining enzyme in % Without base + antioxidant Protease 62 (base only) Lipase 67 Base+25 mmol/l ascorbic acid Protease 82 (0.044% by weight) Lipase 75 Base + 2.5 mmol/l BHA Protease 74 (0.045% by weight) Lipase 76 Base + 2.5 mmol/l BHT Protease 68 (0.055% by weight) Lipase 68

Table 2a shows that enzyme activity is higher when antioxidants are used.

Example 2

Samples of liquid detergents containing protease and lipase (see Table 1 above) were placed in 2.54 cm diameter sealed-top glass jars and exposed to UV radiation at 254 nm and 110 microwatts/ ^cm2 (5 days, 71 cm from the light source). After every 24 hours, the samples were weighed and opened to replace evaporated water. The enzyme activity of the samples exposed to UV light was measured using appropriate substrates. The residual activity was expressed as a percentage of the original activity of the sample before UV irradiation. The samples contained 12.5 mmol/L ascorbic acid, 12.5 mmol/L BHA, or 12.5 mmol/L BHT as preservatives. The control sample contained no such preservatives. The results are shown in Table 2b below.

Table 2b

Effect of antioxidants on enzyme stability exposed to UV-C radiation (254nm)

Sample Enzyme After 24 hours, the remaining enzyme in % Without base + antioxidant Protease 53 (base only) Lipase 67 Base + 12.5 mmol/l ascorbic acid (0.22% by weight) Protease Lipase 79 70 Base + 12.5 mmol/l BHT Protease 77 (0.23% by weight) Lipase 70 Base + 12.5 mmol/l BHT Protease 77 (0.28% by weight) Lipase 70

This again proves the effectiveness of antioxidant-containing preparations in protecting enzymes exposed to UV radiation.

Example 3

Similar experiments were performed under the conditions listed in Examples 1 and 2, but using a UV-A/B chamber (UVA = 1.01 mW/cm ² , UVB = 6.17 mW/cm ² lamp). The HDL-containing enzymes and antioxidant protective agents were then exposed to UV light for 4 days. The results are shown in Table 3 below.

Table 3. Effect of antioxidants on enzyme stability when exposed to UV-A/B radiation

Sample Enzyme After 4 days, the remaining enzyme in % Without base + antioxidant Protease 22 (base only) Lipase 0 Base + 12.5 mmol/l ascorbic acid (0.22 wt. Protease 87 % Lipase 21 Base + 12.5 mmol/l BHA Protease 73 (0.23% by weight) Lipase 48 Base + 6.5 mmol/l ascorbic acid (0.11 wt. Protease 90 % + 6.25 mmol/l BHA (0.12% by weight) Lipase 43

The above table demonstrates that the presence of ascorbic acid, BHA, BHT enhanced the stability of both protease and lipase when exposed to UV-A/B radiation, as shown by the values expressed in % of residual enzymes. The results also demonstrate the synergistic effect between the two antioxidants, as shown in the example showing the combined use of ascorbic acid and BHA.

Claims (5)

·#**> — Patent claims 1. A clear or translucent, high-performance liquid formulation bottled in a transparent container, containing: a) between 10 and 85% by weight of a surfactant, which may be an anionic, nonionic, cationic, amphoteric or zwitterionic surfactant or a mixture thereof; b) between 0.001 and 5% by weight of an enzyme, which may be a protease, lipase, cellulase, oxidase, amylase or a mixture thereof; and c) between 0.001 and 3% by weight of an antioxidant; wherein the composition has a light transmittance of at least about 50% at a wavelength of 410-800 nm in a 1 cm cuvette; and the bottle has a light transmittance of at least 25% at a wavelength of about 410-800 nm. 2. The composition of claim 1, which comprises BHT as an antioxidant. 3. The composition of claim 1, which comprises ascorbic acid as an antioxidant. 4. The composition of claim 1, which comprises BHA as an antioxidant. 5. A method for inhibiting the decline of enzyme activity of a transparent or translucent, high-performance enzyme-containing liquid preparation bottled in a transparent glass bottle, comprising: a) between 10 and 85% by weight of a surfactant, which may be an anionic, nonionic, cationic, amphoteric or zwitterionic surfactant or a mixture thereof; b) between 0.001 and 5% by weight of an enzyme, which may be a protease, lipase, cellulase, oxidase, amylase or a mixture thereof; and wherein the composition has a light transmittance of at least 50% at a wavelength of about 410-800 nm in a 1 cm cuvette; and wherein the bottle has a light transmittance of at least 25% at a wavelength of about 410-800 nm, characterized in that the composition contains between 0.001 and 3% by weight of an antioxidant, based on its total weight. The authorized person: DANUBIA Patent and Trademark Office Ltd. Dr. Zoltánná Gárdonyi