JPH05202393A - Water-base liquid cleaning composition - Google Patents

Abstract

PURPOSE: To obtain an aq. liquid cleaning compsn. suitable for an automatic dishwashing machine by compounding a detergency builder, an enzyme, encapsulated bleach particles, a specific amt. of a reducing agent and water of which the amt. is half the compsn.

CONSTITUTION: An aq. cleaning compsn. consists of a detergency builder (A), an enzyme (B), encapsulated bleach particles (C) and a reducing agent (D) and has a water content of less than 55 wt.%, pref., less than 50 wt.% and the component (D) is present in an amt. of 0.01-0.5 wt.%.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous liquid cleaning composition comprising an enzyme and encapsulated bleach particles. Specifically, it consists of an enzyme, encapsulated bleach particles and a reducing agent,
In particular, it relates to an enzymatic aqueous liquid cleaning composition primarily for use in automatic dishwashers.

[0002]

BACKGROUND OF THE INVENTION Encapsulated bleaching, which has a tendency to release a small amount of inactivating amount of oxidant prior to the release of a given (ie, full concentration of bleach) but delays the appearance of the full concentration of oxidant bleach. Release of oxidant bleaching composition in the form of agent particles), biological soil degrading enzyme, and appearance of enzyme inactivating concentration of oxidant bleaching composition until the total concentration of oxidant bleaching composition is released. Cleaning compositions having a combination of bleaching action and enzymatic degradation of biochemical soils consisting of a chemical reducing agent in an amount effective to retard
There is a description in 4,421,664. The preparation of dry solid powder or granular forms of such cleaning compositions is without any problems and with virtually no difficulty with regard to the stable production of the enzyme during storage. However, when such compositions are prepared as aqueous liquids, enzyme storage stability becomes a problem even at mild alkaline pHs where the enzyme normally stabilizes easily.

In the "safe" area, ie gentle dishwashing liquids, data to date show that aqueous liquids containing oxidant bleach capsules (oxidant bleach with either chlorine or oxygen). It has been suggested that inclusion of the enzyme in it is not feasible due to poor enzyme stability caused by even very slight leakage from the bleach capsule into the entire liquid. Only 4 ppm of available chlorine was sufficient to rapidly degrade the total amount of amylase (starch-degrading enzyme), and about 100 ppm of available chlorine contained all Savinase ^R [superscript R: registered trademark] (proteolytic enzyme) activity. It has been found in an aqueous non-phosphoric acid liquid detergent model system for dishwashers containing these.

The addition of a reducing agent, such as sodium sulfite, as a scavenger of oxidizing agents, such as that proposed in US Pat. No. 4,421,664, results in a commercial product with sufficient and cooperative performance of both enzyme and bleach. It does not improve enzyme stability sufficiently to reach it. Clearly, reducing agents in aqueous liquid compositions are not sufficiently effective to trap oxidants for long periods of time.

[0005]

Accordingly, it is an object of the present invention to improve the stability of an aqueous liquid cleaning composition comprising an enzyme and an oxidant bleach in the form of encapsulated bleach particles.

Surprisingly, the composition has two requirements: a water content of less than 55% by weight, and a content of 0.01.
It has been found that the enzyme stability in such aqueous liquid cleaning compositions can be substantially improved if the requirement of containing a reducing agent in an amount of from 0.5% to 0.5% by weight is met.

[0007]

Accordingly, the present invention is an improved aqueous liquid cleaning composition comprising a cleaning builder, an enzyme, encapsulated bleach particles and a reducing agent, wherein the composition comprises less than 55% by weight, It preferably has a water content of less than 50% by weight and the reducing agent is from 0.01% by weight to 0.
Provided is an improved aqueous liquid cleaning composition consisting of a cleaning builder, an enzyme, encapsulated bleach particles and a reducing agent, characterized in that it is present in an amount of 5% by weight.

Here, the "aqueous liquid" is about 10-55.
By low-viscosity liquids to high-viscosity liquids and also gels and pastes having a water content of wt.%, Preferably 25-55 wt.%, More preferably 35-50 wt. Preferably, the composition of the present invention is a mild alkaline aqueous liquid.

The term "gentle" as used herein means that the composition of the stock solution has a pH of about 5.0 to about 10.5, preferably about 6.5 to about 10.5, and more preferably about 8 to 9.5. Say you have.

Detergent Builders The soluble detergent builder salts useful herein may be in the polyvalent inorganic and polyvalent organic types, or mixtures thereof. Examples of preferred water-soluble compounds include, but are not limited to, examples of inorganic alkaline cleaning builder salts: alkali metal carbonates, boric acid alkali metal salts, phosphoric acid alkali metal salts,
Examples thereof include alkali metal polyphosphates, alkali metal tripolyphosphates, alkali metal bicarbonates and alkali metal silicates. Specific examples of such salts include sodium tetraborate, potassium tetraborate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium tripolyphosphate, potassium tripolyphosphate, sodium orthophosphate. , Potassium orthophosphate, sodium hexametaphosphate and potassium hexametaphosphate.

Examples of preferred organic alkaline cleaning builder salts include (1) water-soluble aminopolyacetic acid salts such as ethylenediaminetetraacetic acid sodium salt, ethylenediaminetetraacetic acid potassium salt, nitrilotriacetic acid sodium salt, nitrilotriacetic acid potassium salt, N- (2 -Hydroxyethyl) nitrilodiacetic acid sodium salt and N-
(2-hydroxyethyl) nitrilodiacetic acid potassium salt;
(2) Water-soluble phytate, such as sodium phytate and potassium phytate; (3) Water-soluble polyphosphonate, such as sodium ethane-1-hydroxy-1,1-diphosphonate, ethane-1- Hydroxy-
1,1-diphosphonic acid potassium salt, ethane-1-hydroxy-1,1-diphosphonic acid lithium salt, methylene diphosphonic acid sodium salt, methylene diphosphonic acid potassium salt, methylene diphosphonic acid lithium salt and the like can be mentioned. ..

Further organic builder salts useful in the present invention include water-soluble alkali metal salts of mellitic acid, water-soluble alkali metal salts of citric acid, water-soluble alkali metal salts of dipicolinic acid and water-soluble oxydisuccinic acid. Examples include polycarboxylic acid salt materials described in US Pat. No. 2,264,103, which include a soluble alkali metal salt and a water-soluble alkali metal salt of alkenyl succinic acid. Polymers and copolymers of water-soluble polycarboxylic acid salts as described in US Pat. No. 3,308,067 are also suitable for the present invention.

Although the above-mentioned alkali metal salt builder of inorganic and organic polyvalent anions are preferable for the use of the present invention in terms of cost, ammonium, alkanol ammonium, such as triethanol ammonium, of any of the above builder anions can be used. Water-soluble salts such as diethanolammonium are useful in the present invention.

Another suitable system for builders is the so-called water insoluble calcium ion exchange builder material.
Examples include various types of water-insoluble crystalline aluminosilicates or water-insoluble amorphous aluminosilicates,
Among them, zeolite is a well-known representative. Other useful materials include Hoechst under the trademark SKS-6.
Laminated silicates such as the products marketed by the company.

Mixtures of organic and / or inorganic builder salts can be used in the present invention.

While any of the polyvalent builder materials are useful in the present invention, the compositions of the present invention are preferably non-phosphate builders for environmental and ecological reasons.

Preferred builders for use in the present invention are sodium citrate, sodium carbonate and sodium bicarbonate and mixtures thereof, or potassium salts thereof. The potassium salt is preferable in terms of solubility.

The amount of builder in the composition is preferably about 5% to 60% by weight, more preferably 25% to about 40% by weight.

Enzymes Enzymes are used for many purposes in various fields where biochemical reactions occur. Generally, an enzyme can be said to be a catalyst capable of promptly carrying out a biochemical reaction, and can be classified according to the type of reaction catalyzed. Enzymes are characterized by a high specificity, ie that each enzyme can catalyze a single reaction of one substance or a very small number of closely related substances.

Examples of enzymes suitable for use in the cleaning compositions of the present invention include lipases, peptidases, amylases (starch-degrading enzymes) and to more easily remove stains or stains from the item being washed. Others include biochemical stains and stains that are encountered in the cleaning scene, which decompose, alter or facilitate the decomposition or alteration action to further remove stains or stains in subsequent cleaning steps. .. Both degradation and alteration effects can improve dirt removal capabilities. Well-known and preferred examples of these enzymes are proteases, lipases and amylases. Lipases are classified in EC class 3, hydrolases, subclass EC 3.1, preferably carboxylic acid ester hydrolase EC 3.1.1. One example thereof is lipase EC3., Which has the taxonomic name glycerol ester hydrolase.
It is 1.1.3. Amylase is the same class as lipase,
Subclass EC 3.2, in particular 3.2.1.1 with the taxonomic name α-1,4-glucan-4-glucanohydrolase.
belongs to EC 3.2.1 glycoside hydrolases such as α-amylase and 3.2.1.2 β-amylase having the class name α-1,4-glucan maltohydrolase. Proteases are the same class as lipases and amylases, the subclass EC3.4, in particular EC3.4.0, such as EC3.4.4.16, which has the taxonomic name subtyropeptidase A.
4.4 Belongs to peptide hydrolase.

Obviously, the scope of the present invention is not limited by the type described above. Further, in the practice of the present invention, in consideration of the composition of biochemical soil, the specific intended soil composition, and the availability of an enzyme that decomposes or modifies soil, the enzyme is selected from a group of enzymes having different functions. Can be used.

The lipase, sometimes called esterase, is
Breaks down greasy dirt. Suitable lipases for use in the present invention include those derived from animals, plants and microorganisms. Also, preferred lipases are found in numerous bacterial and fungal strains. For example, lipases suitable for use in the present invention include Pseudomonas, Aspergillus, Pneumococcus,
Staphylococcus, poisonous bacteria, Mycobacterium Tuberculosi
s, Mycotorula Lipolytica, and Sclerotinia microbial populations, and can be prepared using recombinant DNA techniques.

Preferred animal lipases have been found in body fluids and organs of many species. A preferred system of animal lipases for the present invention is pancreatic lipase.

The lipase is present in the cleaning composition on a pure enzyme basis from about 0.005% to about 10% of the cleaning composition.
%, Preferably 0.01% to 5%.

The enzyme most commonly used in dishwashing compositions is a starch degrading enzyme.

The starch degrading enzyme for use in the present invention is derived from bacteria or fungi. A preferred amylolytic enzyme is Bacillus licheniformis strain NCIB806.
1, NCIB8059, ATCC6334, ATCC6
598, ATCC 11945, ATCC 8480 and A
Cultured from TCC9945A, British Patent Specification No. 1,29
The enzyme prepared and described in 6,839. Examples of such starch degrading enzymes include Novo Co. (Copenhagen,
There is a starch degrading enzyme manufactured and marketed under the trade name of SO-95 ^R or Termamyl ^R from Denmark). Normal,
These amylolytic enzymes are supplied as particles,
About 2 maltose units / mg to 10 maltose units / m
g of enzyme activity.

Starch-degrading activity is measured by the method of Enzymolog
It can be measured by the method as described by P. Bernfeld on page 149 of Vol.

The composition of the present invention also preferably contains a proteolytic enzyme.

Examples of preferred proteolytic enzymes include Gi
Obtained from specific strains of B. Subtilis and B. licheiformis, such as subtilisin Maxatase ^R commercially available from st-Brocades NV (Delft, The Netherlands) and subtilisin Alcalase ^R commercially available from Novo (Copenhagen, Denmark) There is a subtilisin that is used.

Particularly preferred are the commercially available trade names under the trade names Esperase ^R and Savinase ^R from Novo, 8
It is a protease obtained from a strain of Bacillus with maximum activity in the pH range of -12. The preparation of these and similar enzymes is described in British Patent Specification No. 1,243,784.

[0031] Other preferred proteases useful in the present invention, such as described in WO-A-89/06279, there is a product which is commercially available from Novo quite recently tradename Durazym ^R. These enzymes can exist as particles, such as malm, prill, T-particles, etc., and can have an enzyme activity of about 500 glycine units / mg to 1700 glycine units / mg. The proteolytic activity is
urnal of General Physiology, Vol. 22 (1938) 7
It can be measured by the method as described by ML Anson on page 9 (1 Anson unit / g = 733 glycine unit / mg). In addition, enzyme preparations are easy to handle, for example Termamyl 300 L, Savinase 16.0 L, Savi
Commercially available as a liquid or slurry such as nse 16.0 SL.

In all of these enzymes, the starch degrading enzyme of the final composition has a starch degrading activity of 10 ² maltose units / kg to 10 ⁶ maltose units / kg, and the proteolytic enzyme of the final composition has 10 ⁶ glycine units. It can be present in amounts of 0.2% to 5% by weight, respectively, so as to have a proteolytic enzyme activity of / kg to 10 ⁹ glycine units / kg.

Enzyme particles having a low chloride content, for example less than 30% by weight, preferably less than 10% by weight, or substantially zero, are suitable for use in the compositions of the present invention.

Encapsulated Bleach Particles Encapsulation techniques for both peroxygen and chlorine bleaches are known. For example, Johnston in US Pat. No. 4,126,573 shows encapsulation of peroxyacids with water soluble surfactant compounds. U.S. Pat. No. 4,327,151 (Mazolla) which discloses an encapsulated bleaching agent having an inner coating of fatty acid and microcrystalline wax and an outer coating of fatty acid and surfactant Pluronic
And U.S. Pat.
Some patents, such as n), teach the use of coating agents derived from fatty acids. Also, other encapsulated bleaching agents are known. For example, U.S. Pat.
9,764 (Brubaker) is an organic nitrogen-containing halogen bleach,
Figure 3 shows encapsulation of a mixture of NH-containing compounds and hydratable salts of soluble minerals. U.S. Pat.No. 3,036,
013 (Jaszka) teaches encapsulated calcium hypochlorite bleach.

The coating agent is prepared by mixing the coating agent and the compound to be coated in a rotary mill, injecting the coating agent solution or suspension into a fluidized bed of the compound to be coated, in a solvent. It can be provided by various well-known methods such as a method of depositing a coating agent on a compound to be coated which is suspended from a solvent.

The enormous advances in encapsulation technology over the last few years allow the production of chlorine-based or peroxygen-based bleach capsules with outstanding stability. One of these improved techniques uses a wax coating. This is described in EP-A-0,436,971 and in applicant's co-pending European patent application No. 92201091.3. However, the problem is, as mentioned above,
It means that even a slight leak causes enzymatic degradation.

Preferred encapsulated bleach particles for use in the present invention are 3 as described in the aforementioned European patent application.
The paraffin wax comprises a single coating agent particle of paraffin wax of 5 wt% to 55 wt% and a chlorine-based or peroxygen bleaching compound of 45 wt% to 65 wt% as a core. To about 50 ° C, preferably 40 ° C to 50 ° C, with a permeability of 1 at 25 ° C of 1
With 0 mm to 60 mm.

The bleaching agent to be encapsulated in the coating agent may be a chlorine- or bromine-releasing agent or a peroxygen compound. Preferred reactive chlorine- or bromine-oxidizing substances include trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and dichloroisocyanuric acid, and water such as potassium and sodium.
There are heterocyclic N-bromoimides and N-chloroimides, such as their salts with solubilizing cations. Also 1,
Hydantoin compounds such as 3-dichloro-5,5-dimethyl-hydantoin are also very suitable.

Dry granular water-soluble anhydrous inorganic salts such as lithium hypochlorite, sodium hypochlorite, calcium hypochlorite, lithium hypobromite, sodium hypobromite and calcium hypobromite are similarly used. It is suitable for the use of the present invention. Another core material is trisodium chlorinated phosphate. However, chloroisocyanurate is the preferred bleaching agent. Potassium dichloroisocyanurate is sold by Monsanto Company as ACL-59 ^R. Also, sodium dichloroisocyanurate is in the form of dihydrate as ALC-60 ^R from Monsanto, in powder form (particle diameter less than 150 microns; intermediate particle size about 50 microns to 400 mikuns; larger particle size 150-850 microns). ) By Clearon CDB-56 ^R as Ol
It is available from in. Also, very large particles (85
0-1700 microns) have also been found suitable for encapsulation.

Organic peroxy acids or their precursors are also useful as bleach cores. Peroxyacids that can be used in the present invention are solid, preferably substantially water-insoluble compounds. Here, "substantially insoluble in water" refers to a water solubility of less than about 1% by weight at room temperature. Generally, peroxy acids containing at least about 7 carbon atoms are sufficiently insoluble in water for use in the present invention.

Representative monoperoxy acids useful in the present invention include (i) peroxybenzoic acid and, for example, peroxy-α.
Ring-substituted peroxybenzoic acids such as naphthoic acid; (ii) aliphatic monoperoxy acids and substituted aliphatic monoperoxy acids such as peroxylauric acid and peroxystearic acid; (iii) phthaloylamide peroxycaproic acid (P
AP) and alkylperoxy acids and arylperoxy acids.

Typical diperoxy acids useful in the present invention include (iv) 1,12-diperoxide decanedioic acid (DPD
A); (v) 1,9-diperoxyazelaic acid; (vi) diperoxybrassic acid; diperoxysebacic acid and diperoxyisophthalic acid; (vii) 2-decyldiperoxybutane-1,4-dioic acid Alkyl diperoxy acids and aryl diperoxy acids.

Peroxyacid bleach precursors are well known to those skilled in the art. The present invention is not limited to these examples, but for example, N, N, N ', N'-tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonic acid as described in US Pat. No. 4,751,015. Mention may be made of sodium (SNOBS), sodium benzoyloxybenzene sulfonate (SBOBS) and cationic peroxy acid precursor (SPCC).

Further, a compound which produces inorganic peroxygen is suitable as the core of the particles of the present invention. Examples of these materials include monoperoxysulfate, peroxyborate monohydrate, peroxyborate tetrahydrate, and peroxycarbonate.

Manganese composites such as those described in EP-A 0458397, eg Mn-Me TACN or US Pat.
If optionally included a bleaching catalyst such as the sulfonimines described in 041,232 and 5,047,163, it is
It can be present in the form of a second encapsulation independent of the bleach capsule.

The amount of the encapsulated chlorine bleach used in the composition of the present invention is about 0.5% as available chlorine (Avcl).
Can be varied within the range of about 3%. The preferred range for peroxygen bleach is 0.5% to 3% as available oxygen (avO).

Reducing Agents Oxidizing Agents Reducing agents useful for preventing the bleaching compound from reaching enzyme inactivating concentrations include substantially Cl ₂ , HClO.
And other chlorine oxide-containing compositions capable of reducing to Cl ⁻ ions or substantially reducing hydrogen peroxide or peroxyacid bleaching agents to non-oxides. The reducing agent should not damage the object or substance to be washed and should not substantially chemically change either the enzyme or the ingredients of the cleaning composition such as detergents, builders, etc. Is.

Useful reducing agents are reducing [sulfur-oxygen] acids and salts thereof. The most preferable ones are ammonium sulfite ((NH ₄ ) ₂ SO ₃ ), sodium sulfite (Na ₂ S) in terms of availability, low price and high performance.
O ₃ ), sodium bisulfite (NaHSO ₃ ), sodium metabisulfite (Na ₂ S ₂ O ₃ ), potassium metabisulfite (K ₂ S ₂ O ₅ ), lithium hydrogen sulfite (Li ₂
Alkali metal and ammonium salts of (sulfur-oxygen) acids, such as S ₂ O ₄ ), with sodium sulfite being particularly preferred.

Another useful reducing agent is ascorbic acid, which is not particularly preferable in terms of cost. These reducing agents should be used in amounts that are effective enough to capture the lost chlorine or oxidant bleach.
Of course, these amounts will vary from case to case depending on the type and quality of the encapsulated bleach particles,
Generally, a range of about 0.01% to about 0.5% by weight, preferably about 0.02% to about 0.2% by weight is sufficient. In the case of sodium sulfite, an amount of less than 0.01% by weight is not effective, an amount of more than 0.5% by weight is not required and is unwelcome due to its odor.

Optional Ingredients Optional ingredients include, for example, well-known enzyme stabilizers such as polyalcohols (eg glycerol) and borax, antiplaque agents, crystal growth inhibitors, threshold agents,
There are thickeners, fragrances and dyes.

A small amount of a low foaming nonionic surfactant containing an alkoxylated nonionic surfactant, wherein the alkoxy moiety is selected from the group consisting of ethylene oxide, propylene oxide and mixtures thereof; Non-foaming nonionic surfactants are preferably used to improve detergency and to control excessive foaming due to some protein stains. However, the use of excess proportions of nonionic surfactants should be avoided. Usually 0.1 to 7% by weight, preferably 0.5 to 5% by weight is sufficient.

Examples of nonionic surfactants suitable for use in the present invention include Plurafac commercially available from Eurane.
^R RA series, Lutensol ^R LF commercially available from BasF
Series, Triton ^R commercially available from Rohm & Haas
DF series and Synperonic commercially available from ICI
There are ethoxylated, propoxylated, straight chain alcohols of low foaming to non-foaming s.

Other optional but highly preferred additive components having multifunctional properties, especially in non-phosphoric acid compositions, have a molecular weight of 1,000 to 2,000,000 and are acrylic acid, maleic acid, or salts or salts thereof. Anhydrous, vinylpyrrolidone methyl- or vinylpyrrolidone ethyl-,
May be homopolymers or copolymers of vinyl ethers and other polymerizable vinyl monomers, 1 wt% to 15%
There is a weight percentage of polymeric material, preferably about 5 weight percent. Preferred examples of such a polymer include polyacrylic acid or polyacrylic acid ester; polymaleic acid or polymaleic acid ester; polymaleic acid / acrylic acid copolymer; 70:30 acrylic acid / hydroethyl maleic acid ester copolymer; 1: 1 styrene / maleic acid copolymer; isobutylene / maleic acid and diisobutylene /
Maleic acid copolymers; methyl vinyl ether / maleic acid copolymers and ethyl vinyl ether / maleic acid copolymers; ethylene / maleic acid copolymers; polyvinylpyrrolidone; and vinylpyrrolidone / maleic acid copolymers. Although these polymers are believed to function as auxiliary builders, they can also function as the primary builder under certain conditions.

The compositions of the present invention may also comprise a thickening agent, for example a polymer (or copolymer thereof) such as the preferred acrylic or methacrylic acid esters, or a cellulose such as hydoxymethylcellulose. , That is preferable. The typical content level of the thickener is
0.1% to 10% by weight of the total composition, eg 0.5
% To 5% by weight.

Buffering agents may be necessary to adjust and maintain the alkalinity and pH of the composition at the desired levels. These are, for example, alkali metal carbonates, alkali metal bicarbonates and borate alkali metals. It is also possible to use sodium hydroxide and / or potassium hydroxide.

[0056]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

[0057] was prepared in Example 1 following aqueous liquid automatic dishwashing composition: Composition I wt% Carbopol ^R 941 1.50 NaOH (pellets) 0.80 Borax 3.00 Glycerol 6.00 Polymer (Sokalan ^R CP7) 5.00 Sodium citrate 30.00 Sodium sulfite 0.04 Chlorine bleach capsule 1) 4.30 Proteolytic enzyme (Savinase ^R 16.0L) 0.30 Amylase (Termamyl ^R 300L) 0.30 Water 100.00 (approx. 49%) 1) The chlorine bleach capsule used here is , About 50% Na-DCCA nuclei yielding about 1.2% available chlorine and 50% paraffin wax coating (see EP-AO, 436,971).

If maximum enzyme activity is intended immediately after the end of the treatment process, the order of addition during manufacture should be to add sodium sulfite as soon as possible with the addition of the bleaching capsules and clearly before the addition of the enzyme.

The enzyme stability of the composition is quite satisfactory.

When a similar composition containing 20% sodium citrate was prepared, which resulted in a water content of about 59% by weight, a substantial reduction in enzyme stability was observed.

M at a temperature of 55 ° C. using 14 ° FH of water
Composition I was tested in an iele 595SC dishwasher.

Commercial Dutch product “Sun Liqu”
The results of washing compared to "id" and "sun-Progress" are shown in the table below.

[0063]

[Table 1]

Example II In a dishwasher liquid based on the formulation of Example I
The effects of changes in nominal water content on the storage stability of Savinase and Amylase are shown in Figures 1 and 2, respectively (%
so).

FIG. 1-5. At room temperature (+) and 37 ° C. (.)
The residual water content (%) of Savinase was plotted on the vertical axis against the nominal water content (% by weight) of the liquid product after storage for 5 weeks.

FIG. 2-at room temperature (+) and 37 ° C. (.)
The residual activity (%) of Amylase was plotted on the vertical axis against the nominal water content (% by weight) of the liquid product after storage for 5 weeks.

These figures show a clear improvement in enzyme storage stability in compositions containing less than 55% water. In particular, Figure 1 shows a dramatic decrease in Savinase residual activity in compositions containing 55% or more water.

Example III Three aqueous liquid cleaning compositions consisting of the following ingredients were prepared with varying amounts of sulfurous acid.

[0069] The composition III wt% Carbopol ^R 941 1.50 NaOH (pellets) 0.80 Borax 3.00 Glycerol 6.00 Polymer (Sokalan ^R CP7) 5.00 Sodium citrate 30.50 Sodium sulphite 0.00-0.04-0.10 MPS bleach capsules 1) 5.00 Proteolytic enzyme (Savinase ^R 16.0L) 0.30 Amylase (Termamyl ^R 300L) 0.30 Water 100.00 (approx. 47%) 1) The MPS bleaching capsule used here is monopersulfate as the core bleaching substance. 5 to potassium (50% by weight)
0% by weight paraffin wax coating encapsulating agent, prepared according to the method as described in EP-AO, 436,971.

After storing these compositions at 37 ° C. for 6 weeks, the residual activities of Savinase and Termamyl were measured.

In the case of 0.00% sulfite, the Savinase residual activity (%) is 30%, and in the case of 0.04% sulfite, Savina
The se residual activity (%) is 80%, and in the case of 0.10% sulfite, the Savinase residual activity (%) is 75%.

In the case of 0.00% sulfurous acid, Amylase (Terma
myl) residual activity (%) is 0%, in the case of 0.04% sulfite, Amylase (Termamyl) residual activity (%) is 95%,
In the case of 0.10% sulfite, Amylase (Termamyl) residual activity (%) is 95%.

These results indicate that low levels of water are not the only attribute of stable enzyme storage, and the presence of sulfite is essential even at water levels below 55%.

Example IV This example demonstrates enzyme stability as a function of sulfite level in accelerated storage tests. The experiment was conducted using the formulation of Example I and varying the level of sodium sulfite. This composition was stored at 50 ° C. for 6 hours. The results are shown in the table below.

[0075]

[Table 2]

[Brief description of drawings]

1 shows the nominal water content (% by weight) of liquid products after storage for 5.5 weeks at room temperature (+) and 37 ° C. (.),
It is the figure which plotted the residual activity (%) of Savinase on the vertical axis.

FIG. 2 shows the relative water content (% by weight) of the liquid product after storage for 5.5 weeks at room temperature (+) and 37 ° C. (·),
It is the figure which plotted the residual activity (%) of Amylase on the vertical axis.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C11D 7:42 7:54)

Claims (8)

[Claims] 1. An aqueous liquid cleaning composition comprising a cleaning builder, an enzyme, encapsulated bleach particles and a reducing agent, comprising:
Detergent builders, enzymes, encapsulated bleaches, characterized in that the composition has a water content of less than 55% by weight and the reducing agent is present in an amount of 0.01% to 0.5% by weight. An aqueous liquid cleaning composition comprising particles and a reducing agent. 2. The cleaning builder according to claim 1, characterized in that the water content is less than 50% by weight.
An aqueous liquid cleaning composition comprising an enzyme, encapsulated bleach particles and a reducing agent. 3. The amount of reducing agent is 0.02% by weight to 0.2.
% Or claim 2 characterized in that it is% by weight.
An aqueous liquid cleaning composition comprising a cleaning builder, an enzyme, encapsulated bleach particles and a reducing agent as described in 1. 4. The wash builder, enzyme, encapsulated bleach particles and reduction according to claim 1, 2 or 3, characterized in that it has a pH of about 5.0 to 10.5. An aqueous liquid cleaning composition comprising an agent. 5. Aqueous solution comprising a washing builder, an enzyme, encapsulated bleach particles and a reducing agent according to any one of claims 1 to 4, characterized in that the reducing agent is sodium sulfite. Liquid cleaning composition. 6. A starch-degrading enzyme is included,
An aqueous liquid cleaning composition comprising a cleaning builder, an enzyme, encapsulated bleach particles and a reducing agent according to any one of claims 1 to 5 above. 7. The method according to any one of claims 1 to 5, which contains a proteolytic enzyme,
An aqueous liquid cleaning composition comprising a cleaning builder, an enzyme, encapsulated bleach particles and a reducing agent. 8. An aqueous liquid consisting of a washing builder, an enzyme, encapsulated bleach particles and a reducing agent according to claim 6 or 7, characterized in that it contains a mixture of a starch degrading enzyme and a proteolytic enzyme. Cleaning composition.