KR960010589B1 - Detergent additive for bleaching fabric - Google Patents

Abstract

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Description

[Name of invention]

Detergent additives for bleaching fabrics

Detailed description of the invention

[Field of Invention]

The present invention relates to a method of bleaching a fabric by treating the fabric with a detergent additive comprising an enzyme system capable of exhibiting a bleaching effect on the fabric during the cleaning process, a detergent composition containing the detergent additive and an enzyme exhibiting a bleaching effect. It is about.

[Background of invention]

It is well known in the art to use bleach as a constituent of detergent compositions in cleaning processes. So bleach is usually incorporated or marketed as a constituent of the major parts of commercially available detergent compositions.

An important bleach typically incorporated into detergent compositions is a compound that acts as a precursor of hydrogen peroxide formed in the process of cleaning procedures. Perborate and percarbonate are applied as detergent additives and are the most important examples of compounds that exhibit a bleaching effect in this way. The detailed mechanism of perborate and percarbonate bleaching is currently unknown, but hydrogen peroxide converts colorants that color fabrics by oxidation into uncolored materials, and oxidation of the colorants results from their direct interaction with perborate or percarbonate. It is usually estimated that this may happen.

While these conventional bleaching systems have been widely accepted and have been very satisfactory in many examples, there have been several attempts to improve their performance over the years.

An important purpose is to provide a bleaching system which works at low temperatures and which is generally more effective than conventional systems.

It is also an important objective to develop a system that results in better utilization of the bleach used in bleaching of textiles or otherwise used in detergent compositions.

In particular, these developments have been urged to perform cleaning at low temperatures, not at least the optimum operating temperature of at least 60 ° C, at the request of the consumer for the operation of conventional bleaching systems. There has been a call for environmental considerations that release excess bleach into the environment that is not fully used in the procedure's process.

In relation to these attempts to develop improved bleaching systems, considerable surroundings have been derived for the possibility of generating bleach types that have a powerful effect during cleaning by hydrogen peroxide from conventional precursors such as perborate and percarbonate.

An example of the successful development of this series is the TAED (tetraacetylethylenediamine) based system currently widely used in detergent compositions.

(See, e.g., Second World Conference on Detergents, A. R. Baldwin (ed.), American Oil Chemists' Society, 1987, pp. 177-180)

[Overview of invention]

Surprisingly, it has been found that the application of a group of enzymes (usually called peroxidase) that utilizes hydrogen peroxide as a substrate for the oxidation of organic or inorganic substances can enhance the bleaching effect of hydrogen peroxide during the sejong process. .

Therefore, the present invention relates to a detergent additive comprising an enzyme that can exert a bleaching effect on the fabric and exhibit an effect of peroxidase action.

Detergent additives of the present invention usually comprise hydrogen peroxide or a precursor of hydrogen peroxide, preferably perborate or percarbonate.

In the present specification, the term "enzyme showing an effect of peroxidase" refers to an enzyme having a mode of action similar to that of peroxidase, and is used synonymously.

Peroxidases are well known in the art (e.g., B. C. Saunders et al, Peroxidase, London, 1964, p 10 ff.), Which act on several amino and phenolic compounds resulting from color production.

In this regard, it should also be taken into account that peroxidase can exert a bleaching effect on the coloring matter.

Mechanisms to control the ability of peroxidases to act to bleach colored stains present on fabrics caused by such colorants have not yet been identified, but in general these enzymes reduce hydrogen peroxide (substrate 1) and It is believed to act by oxidizing the coloring material of the colored contaminant (substrate 2) to produce a colorless material which eventually discolors the fabric. This reaction is shown in Table 1 below.

Scheme 1:

Donor (substrate 2) + H ₂ O ₂ → oxidized donor + 2H ₂ O

Peroxidases generally exhibit affinity for coloring substances present in colored contaminants that act as substrates for enzymes (these are typically natural dyes such as many polyphenols), so excess hydrogen peroxide is achieved to achieve a suitable bleaching effect. Bleaching can be targeted to pigmented contaminants because more effective utilization of hydrogen peroxide can be obtained by applying peroxide enzymes for bleaching than conventional bleaching methods that must be present.

This suggests that the use of the detergent composition of the present invention to bleach colored contaminants on fabrics can reduce the amount of hydrogen peroxide or its precursors in detergent compositions or additives containing additives and can nevertheless provide satisfactory bleaching effects. it means.

Thus, when the detergent additive of the present invention is applied for bleaching, the environmental load released to the environment, that is, the amount of unused bleach can be reduced.

In addition, smaller amounts of hydrogen peroxide need to be added to achieve effective bleaching, so the full performance of detergent compositions containing such bleaching agents (eg, detergent enzymes tend to be degraded when excess bleach is applied). Can be improved.

Peroxidases that are specific for certain colorants (e.g., betaine, carotenoids, flavonoids, etc.) can be used for specific purposes, while peroxidases of low specificity (e.g., for many natural colorants) It is believed that it can be used for more nonspecific enzyme bleaching.

Peroxidase has already been reported to be able to discolor certain pigments (see, eg, W. Schreiber, Biochem. Biophys. Res. Commun, which describes the degradation of 3-hydroxyflavones by Hosredish peroxidase). 63 (2), 1975, pp. 509-514; A. Ben Aziz, which describes the bleaching of carotene by peroxidase, Pytochemistry 10, 1971, pp. 1445-1452; and bleaching of betaine by horseradish peroxidase BP Wasserman, J. Food Sci., 49, 1984, pp. 536-538).

All of these publications describe test methods for incubating the pigment with enzymes in solution. In any case, the publications therefore contain air to allow the coloring material to be absorbed or partially absorbed into the fabric's fibers so that the coloring material is less enzymatic, or to allow the coloring material to be generated other than what is actually inherent in the dye solution. It does not indicate that peroxidase can be effective in bleaching dry colored contaminants in fabrics that can be oxidized by oxygen.

In addition, Ben Aziz et al. And Wasserman et al. Proposed the bleaching of peroxidase for carotene and betaine, respectively, as a problem when using these pigments as food colorants, which said that the problem should be prevented by the inclusion of antioxidants in the foodstuff. .

So they do not regard the peroxidase-modulated bleaching of these pigments as having essentially any practicality.

In contrast, US Pat. No. 4,690,895 discloses bleaching paper pulp by peroxidase.

[Detailed Disclosure of the Invention]

Peroxidases that can be applied for this purpose as detergent additives can be produced and isolated from microorganisms or plants (eg, horseradish peroxidase) such as basidiomycetes, fungi, radiation fungi or bacteria.

Some preferred microorganisms include, in particular, strains of Fusarium, such as Fusarium oxyspourm, especially Streptomyces such as Streptomyces thermoviolaceus or Streptomyces biridosporus. Strains of Myces, in particular strains of Pseudomonas, such as Pseudomonas putida or Psendomonas fluorescens, Coprinus cinereus, Coprinus macronerus Coprinus macrorhizus or Coprinus cinereus f. Strains of Coprinus cinereus f. Microsporus, in particular Strepto Bertisilium Bertisilium ssp. Strains of Streptoberticillium, such as Verticillium, in particular strains such as Bacillus stearothermophilus, in particular strains of Coriorus such as Coriolus versicolor Strains of Panerochaete such as Panerochatea chrysosporium are included.

Particular examples of preferred strains include Coprineus cinerea F. a. Microsporus IFO 8371. Coprinus cinereus IFO 30114, Pseudomonas fluorescens NRRL B-11, Streptoverticillium vertisilium ssp. Bertisilium IFO 13864, Streptomyces thermobioaces viridos forus ATCC 39115, Streptomyces batius ATCC39117, Streptomyces CBS 278.66, Streptomyces paeochromogenes NRRL B-3559, Schudomonas pylori Nia ATCC 15958, Fusarium Oxysis Forum DSM 2672, and Basilius Steahromophilus ATCC 12978.

Other potential sources of useful peroxidases are B.C. Saunders et al., Op. cit., pp. 41-43.

Particularly preferred peroxidases are those that are active at the typical pH of the wash liquor, ie, pH 6.5-10.5, preferably pH 6.5-9.5, more preferably pH 7.5-9.5. More specifically, the peroxidases related to this purpose are those that exhibit at least 25% of their optimal activity (ie their activity at pH optimum) in the pH range as measured by the ABTS assay described in Example 1 below. to be.

Such peroxidases can be isolated by screening for peroxidase products by pro-alkaline microorganisms, for example by the ABTS assay described in Example 1 below.

Other preferred peroxidases exhibit good thermal stability, especially their stability to commonly used detergent compositions such as nonionic, cationic or nonionic surfactants, detergent enhancers, phosphates and their initiation after 20 minutes at about 40 ° C. Retaining at least 25% of their activity, in particular those having at least 25% of their starting activity after exposure to the detergent component for 20 minutes.

Methods for preparing enzymes used in accordance with the present invention are described, for example, in FEBS Letters 1625, 173 (1), Applied Environmental Microbiology, 1985, 2. pp. 273-278, Applied Microbiol. Biotechnol. 26, 1987, pp. 158-163, Biotechnology Letters 9 (5), 1987, pp. 357-360, Nature 326, 1987, 4. 2., FEBS Letters 4270, 209 (2), p. 321 and the like.

Another group of useful peroxidases is composed by ligninase; These enzymes, which exhibit strong peroxidase activity, help lower lignin (eg wood) and are produced by various wood rot bacteria.

They have already been suggested for bleaching paper pulp (for example, US Pat. No. 4,690,895).

Useful peroxidases are also halogen oxidases such as chloro- and bromoperoxidases, because they can oxidize halogen ions with the bleach, a powerful bleach, apart from being able to oxidize organic compounds.

The peroxidase is a DNA sequence encoding a function that allows the expression of the peroxidase and permits the expression of the DNA sequence encoding the peroxidase in a medium under conditions of recovering the peroxidase from the medium and the DNA sequence encoding the peroxidase. It can be produced by a method comprising culturing a host cell modified with a recombinant DNA vector to perform the.

For example, the DNA moiety encoding peroxidase establishes a cDNA or genomic library of peroxidase-producing microorganisms such as one of the microorganisms described above, and the oligonucleotide prowood synthesized based on the pre or partial amino sequence of the peroxidase. By screening for positive clones by conventional procedures, such as hybridization, or by selecting clones that exhibit appropriate enzymatic activity, or clones that produce a platen that reacts with the antibody to the native peroxidase. Can be isolated.

When selected, the DNA sequence can be inserted into a suitable replicable expression vector consisting of a replicator capable of replicating the vector in the host organ in question and a suitable promoter, operator and terminator that allows the peroxidase to be expressed in the particular host organ.

The resulting expression vector is then a suitable host cell, such as a preferred example fungal cell of the type Aspergillus, preferably Aspergillus oryzae or Aspergillus niger. It can be transformed into.

Fungal cells may themselves be modified in a known manner by processes involving regeneration of the cell wall, followed by modification of the protoplasts and protoplast formation.

The use of Aspergillus as a host microorganism is described in EP 238,023 (Novo INDUSTRIA A / S), the contents of which are incorporated herein by reference.

Alternatively the host organ may be a bacterium, in particular Streptomyces and Bacillus or strains of E, coli.

Modification of bacterial cells can be carried out according to conventional methods as described in T. Maniatis et al., Molecular Clonin: A Laboratory Manual, Cold Spring Harbor, 1982.

In addition, the structure of the appropriate vector and the selection of the DNA sequence is standard procedure, reference is made to T. Maniatis et al., Op. can be executed by cit.

The medium used to culture the modified host cell may be any conventional medium suitable for growing the present host cell.

Expressed peroxidases are conveniently secreted into the medium and can be recovered from them by conventional known procedures, which include separating cells from the medium by centrifugation or filtration, while precipitating the protein components of the medium with salts such as ammonium sulfate. And chromatographic procedures such as ion exchange chromatography, affinity chromatography, and the like.

Due to the possibility of reducing the amount of hydrogen peroxide required for bleaching stains on textiles by applying the above-mentioned peroxidase, it is difficult to generate a sufficient amount of hydrogen peroxide. The process can be utilized. Thus, the detergent additive according to the present invention may further include an enzyme system (that is, an enzyme and a substrate thereof) capable of generating hydrogen peroxide.

One category of hydrogen peroxide systems consists of oxidases and oxidized substrates, which can convert oxygen molecules and organic or inorganic substrates to hydrogen peroxide. These enzymes are of no use or limited in bleaching stained stained fabrics because these enzymes generate very small amounts of hydrogen peroxide, but the detergent additives of the present invention as a sufficient utilization of the hydrogen peroxide produced as described above is ensured by the presence of hydrogen peroxide. Can be used to advantage.

Preferred oxidases are those that act on inexpensive and readily available substrates that can be conveniently included in detergent compositions.

An example of a substrate, however, is glucose, which can be utilized for the production of hydrogen peroxide by glucose oxidase.

Other suitable oxidases include urate oxidase, galactose oxidase, alcohol oxidase, amine oxidase, amino acid oxidase and cholesterol oxidase.

Detergent additives of the invention may be in the form of non-dusting granules, liquids in particular stable liquids or protected enzymes.

Non-dusty granules can be prepared as described in US Pat. Nos. 4,106,991 and 4,661,452 (both NovoIndustri A / S applications) and can be optionally coated by all known methods.

The preparation of liquid enzymes can be stabilized by, for example, adding polyols such as propylene glycol, sugar or sugar alcohols, lactic acid or boric acid according to established methods.

Other enzyme stabilizers are well known in the art.

Protected enzymes can be prepared according to the methods described in EP 238,216.

Detergent additives may further comprise one or more other enzymes such as proteases, lipases or amylases that are commonly included in detergent additives.

In another aspect, the present invention relates to a detergent composition comprising hydrogen peroxide or a precursor thereof, preferably perborate or percarbonate and an enzyme exhibiting peroxidase activity.

These and other ingredients (e.g., oxidase and substrates thereof) essential and / or beneficial for achieving bleaching of stained stained fabric can be added to the detergent composition individually or in the form of detergent additives as described above. May be included.

The detergent composition of the present invention also includes a surfactant which may be of anionic, nonionic, cationic or zwitterionic type and mixtures of these surfactants.

Representative examples of anionic surfactants include linear alkylbenzenesulfonates (LAS), alphaolefinsulfonates (AOS), alcoholethoxysulfates (AES) and alkali metal salts of natural fatty acids.

The detergent composition of the present invention may contain other detergent components known in the art such as, for example, thickeners, corrosion inhibitors, metal ion disintegrants, anti-deposition agents, flavoring agents, enzyme stabilizers and the like.

It is considered that the detergent composition of the present invention may contain peroxidase in an amount corresponding to 0.1-100 mg of peroxidase per liter of washing liquid.

The detergent composition of the present invention may be prepared in any convenient form such as powder or liquid.

The enzyme can be stabilized in a liquid detergent with the inclusion of an enzyme stabilizer as described above. Liquid detergents may also include stabilized hydrogen peroxide precursors.

Usually the solution pH of the detergent composition of the present invention may be 7-12, in some cases 7.0-10.5.

Other detergent enzymes such as proteases, lipases or amylases may be included in the detergent compositions of the present invention either individually or as additives as described above.

In another aspect, the present invention also relates to a fabric bleaching method comprising treating the fabric with a detergent additive or detergent composition as described above. The present invention also relates to a bleaching method for treating a fabric with an enzyme that exhibits peroxidase activity in the presence of hydrogen peroxide or a precursor thereof or in the presence of any oxidase and a substrate for this oxidase.

As described above, this method is very suitable for bleaching colored contaminants caused by natural coloring substances such as polyhydric phenols found in fruit juices, wines, black teas and the like.

The bleaching treatment can be appropriately carried out by dipping, washing or washing.

Detergent additives or detergent compositions can also be applied during textile bleaching, for example during their manufacturing process.

The invention is illustrated more specifically by the following examples, which of course are not intended to limit the scope of the invention.

Example 1

Homogeneously contaminated cotton samples with unsweetened blackcurrant juice were subjected to model cleaning to evaluate the bleaching effect of the horseradish peroxidase + hydrogen peroxide system.

At this level, 10 mmol / l of H ₂ O ₂ (equivalent to about 1.6 g of sodium perborate trihydrate) was found to be beneficial at an application of 5 mg / l of horseradish peroxidase (Boehringer-Mannheim).

The experimental conditions were as follows:

Cleaning solution: adjusted to pH7.5 with 0.01M borax, phosphoric acid

Cleaning process period: 30min

Temperature: 25 ℃

Fabric / liquid ratio: 10g / ℓ

Bleaching Effect Evaluation: The washed specimens were washed with demineralized water and then dried in the dark overnight and then released in the 400-700 nm wavelength range and measured on a Datacolor Elrephometer 2000.

The obtained relative cleaning values are given in the following table, the cleaning function of which is defined as follows.

(R: indicates emission)

The reference treatments were treated with the boric acid solution as described above and did not contain any bleach.

The results of treatment with H ₂ O ₂ 10 mmol / L without peroxidase are shown for comparison.

H2O2 oxidation of ABTS [ABTS = 2,2'-azino-bis (3-ethylbenzthiazoline-6-sulfonic acid), supplied by Boehringer-Mannheim as diammonium salt] at pH 7.5 monitored at 418 nm Analyzes were performed before and after the cleaning experiments by standard techniques included (described in REChilds and WG Bardsley, Biochem. J. 145, 1975, pp 93-103).

Post-cleaning activity was 70% of initial activity.

Example 2

A homogeneously contaminated cotton specimen of sugarless black currant juice and red wine of black tea was model-washed to evaluate the bleaching effect of the horseradish peroxidase / HO system.

The experimental conditions were as follows:

Cleaning solution: 1.6mM Ca 0.05 M sodium phosphate buffer, pH = 7.5, prepared with water of equivalent hardness

Cleaning period: 60min

Temperature: 24 ℃

Bleach: HO 10mM

Enzyme: Sigma P-8125 Horseradish Peroxidase, 2mg / ℓ

Fabric / liquid ratio: 10g / ℓ

Evaluation of the Bleaching Effect: Measurements were made as described in Example 1 except that tap water was used to flush the specimens.

It was found that the cleaning device for treatment with enzyme + HO at 460 nm and the cleaning value for treatment with only H2O2 were as follows.

(These three types of samples were cleaned together and accompanied by uncontaminated samples. The bottom line of the table relates to uncontaminated specimens.)

Similar experiments were conducted at pH8.3 and two pH values in the presence of anionic surfactants (linear alkylbenzenesulfonates) and nonionic surfactants.

None of these alterations significantly affected the bleaching effect, and as monitored by the ABTS assay described in Example 1, the activity of the enzyme in the wash solution was essentially the same in all experiments (relative activity + / -30% or less).

Example 3

Several samples of homogeneously contaminated specimens of beet root juice were used to evaluate the bleaching effect of system HO + peroxidase derived from Coprinus macrorhizus.

The experimental conditions were as follows:

Wash solution: Potassium phosphate buffer solution 0.05M adjusted to pH7.0

Cleaning period: varies as specified below

Temperature: 24 ℃

Fabric / liquid ratio: 11g / ℓ

Hydrogen Peroxide: 0.2mM

Enzyme: Evaluation of 20 mg / L Bleaching Effect Peroxidase Derived from Coprenus Macrorisers (Chemical Dynamics Corporation, New Jersey USA, prod. No. 70-9590-00): Measured as described in Example 2.

The results were as follows.

In experiment (1), washing was performed by immersion overnight, and in experiments (2) and (3), the buffer solution was 1.6 mM Ca. It was prepared with water of hardness equivalent to, in Experiment (1) and (4) was prepared in deionized water buffer.

Claims (9)

(a) enzymes in the form of non-dusty granules, liquids, especially stable liquids or protected enzymes, which exhibit peroxidase activity, and (b) hydrogen peroxide, precursors of hydrogen peroxide, or suitable substrates for oxidase and oxidase. Detergent composition, characterized in that made. The detergent composition according to claim 1, wherein the precursor of hydrogen peroxide is perborate or percarbonate. The detergent composition of claim 1, wherein the peroxidase can be produced by fungi. The detergent composition of claim 1, wherein the peroxidase is active at pH7.5-7.9. A method of bleaching colored contaminants present in a fabric, comprising treating the fabric with a detergent composition according to claim 1. 6. The method of claim 5 wherein the treatment of the fabric is carried out by a dipping, washing or washing process. A method of bleaching colored contaminants present in fabrics, comprising treating the fabric with an enzyme that exhibits peroxidase activity in the presence of hydrogen peroxide, a precursor of hydrogen peroxide, or an appropriate substrate for oxidase and oxidase. The detergent composition of claim 1, wherein the oxidase is a glucose oxidase, urate oxidase, galactose oxidase, alcohol oxidase, amine oxidase, amino acid oxidase or cholesterol oxidase. The detergent composition according to claim 3, wherein the fungus is basidiomycete.