DE19718978A1 - Process for inhibiting color transfer in textiles during washing - Google Patents

Abstract

The invention relates to a method for preventing the colours in dyed textiles from running into other textiles during washing or rinsing in a liquid for washing or rinsing. The invention is characterised in that cyclodextrin, cyclodextrin derivatives or substances which form cyclodextrin or cyclodextrin derivatives in the washing or rinsing liquid are added to said washing or rinsing liquid.

Description

The invention relates to a process for inhibiting the color transfer of colored Textiles on other textiles during washing or rinsing in a wash or Rinsing fluid and a suitable for incorporation in detergents and cleaners Enzyme granules containing enzyme and cyclodextrin, cyclodextrin derivatives and / or in the Washing or rinsing liquid cyclodextrin or cyclodextrin derivatives forming Contains substances, a process for the preparation of the enzyme granules and the Use of the enzyme granules in solid detergents and cleaners.

The transfer of dyes in the common wash of colored and white or light-colored textiles is a long-known problem. At the laundry will be the dyes are at least partially dissolved from colored textiles, and these dissolved color fabrics then settle evenly on all textiles, d. H. also on the white or bright colored textiles again. The prior art will be numerous possibilities be wrote to inhibit or reduce these occurring color transfer.

From the German patent application DE-A-38 03 630 a detergent additive is known, based on a content of at least partially water-soluble polymer components of N-vinylpyrrolidone or N-vinylimidazole or N-vinyloxazolidone in combination with what has water-soluble or water-insoluble cationic compounds.

International Patent Application WO 91/05839 discloses a method for inhibiting the color transfer in the washing of textiles, wherein an enzyme which Peroxidase activity or an enzyme having suitable oxidase activity, the Washing liquid is added. The enzymes are hydrogen peroxide or sow erstoff liberated, which removes the dyes from the textiles in undyed Ver oxidized bonds. This prevents the detached dyes on white or light colored textiles.  

In International Patent Applications WO 93/15174, WO 93/15175, WO 94/11477 and WO 94/25555 describes detergent compositions which promote color transfer each containing a metal catalyst selected from (a) metal porphine and water-soluble or water-dispersible derivatives thereof, (b) metallopor phyrin and water-soluble or water-dispersible derivatives thereof, and (c) metallo phthalocyanine and water-soluble or water-dispersible derivatives thereof. The composition described in international patent application WO 93/15174 Also contains an enzymatic system, which hydrogen peroxide and a polymer such as alkoxy, hydroxy, thiol, amide, heterocyclic amine-containing polymers, polyamines, polyurethanes or polyacrylonitrides.

The composition described in international patent application WO 93/15175 tion contains in addition to the metal catalyst an enzymatic system, which is water forms peroxide, and a compound which prevents the enzymatic oxidation. This compound becomes faster than the enzyme but slower than that of the tissue dissolved dye oxidized, whereby the stability of the enzymes can be increased. As ge suitable connections are z. As tertiary amines and polyamines called.

The composition described in international patent application WO 94/11477 tion contains in addition to the catalyst polyamine N-oxide-containing polymers and an effective Amount of bleach. Described in International Patent Application WO 94/25555 bene composition also contains an effective addition to the metal catalyst Amount of bleaching agent and a lipolytic enzyme which in its amino acid sequence no Contains metheonin.

The compositions described in the aforementioned patent applications tongues exploit the fact that dye removed from the tissue is replaced by water peroxide is oxidized to a colorless compound. This oxidation process can be catalyzed by the said metal catalysts. The color-inhibiting effect is increased by addition of complexing agents.

In international patent applications WO 94/02580, WO 94/02581, WO 94/10277, WO 94/10281, WO 94/11473 and WO 94/11482 are surfactant-containing and optionally  bleach-containing wash and softener compositions described the nitrogen containing polymers wherein the dye transfer of dissolved or suspended Dyes on white or light colored textiles by addition of nitrogen-containing polyme can be prevented or reduced.

In the known from the prior art systems known who the metal catalysts and nitrogen-containing compounds used in part to ecological pollution of the wastewater. In addition, the genann th nitrogen-containing polymers in the production are relatively expensive. Another disadvantage is that these systems consist of several components, what the manufacturing cost the detergent increases.

The present invention was accordingly an object of a method for Inhi Color transfer of dyed textiles to other textiles during the Washing or rinsing in a washing or rinsing liquid, which uses compounds or combination of compounds that are biologically easily degradable and inexpensive to produce. Another task of the present The invention was to find a form suitable for these substances, in which these can be used in detergents and cleaners.

The present invention accordingly provides a method for inhibiting the Color transfer of dyed textiles to other textiles during washing or Rinsing in a washing or rinsing liquid, which is characterized in that the Washing or rinsing liquid cyclodextrin, cyclodextrin derivatives or in the washing or rinsing Rinsing fluid cyclodextrin or cyclodextrin derivatives forming substances added the.

Cyclodextrins, also called cycloglucans, can be used in the breakdown of starch Bacillus macerans or B. circulans under the action of cyclodextrin glycosyltransferase be formed. The cyclodextrins usually consist of 6, 7 or 8 α-1,4-ver linked glucose units. The use of cyclodextrins or their derivatives as active Cleaning component is described for example in the international patent application WO 94/10280 described.  

Surprisingly, it was found that the color transfer in the washing of far washing with the addition of cyclodextrins or their derivatives or substances, which form these compounds in situ in the washing or rinsing liquid can be inhibited can.

In the process according to the invention, all cyclodextrin monomers, for example α-, β-, or γ-cyclodextrin be used. Likewise, all cyclodextrin derivatives are suitable such as cyclodextrin carbonates, ethers or polyethers, or cyclodextrin derivatives in which one or more of the hydroxy groups is substituted by functional radicals are iert. Such functional groups include, for example, methyl, ethyl, hydroxy ethyl, hydroxypropyl or acetyl groups. Particularly suitable are such radicals, by which the water solubility of the cyclodextrin is increased. Also any mixtures cyclodextrin and / or cyclodextrin derivatives may be used.

As substances containing cyclodextrin or cyclodextrin derivatives in situ in the wash or Forming rinse liquid, such substances may be mentioned, which in the presence of Cyclodextrin glycosyltransferase form cyclodextrins. Such substances are included For example, amylose. A combination of cyclodextrin glycosyltransferase and amylose has proved to be particularly advantageous because amylose a cheap and ecologically unbe is thoughtful substance.

The cyclodextrins, cyclodextrin derivatives or the substances forming these compounds can be in an amount of 0.1 to 5.0 wt .-%, preferably from 0.5 to 2.0 wt .-%, bezo to the amount of textiles to be cleaned or rinsed, the washing or rinsing liquids be added. The substances can be used at any time Washing or rinsing process, for. B. added at the beginning or during the process who the.

The substances used according to the invention can be used in any desired, for the washing or Rinsing process suitable form can be added. They are preferred in the form of Granule compounds, d. H. together with other substances, such as. As enzymes, added puts. The use of compounds that contain multiple active components is off economic reasons for the production of detergents and cleaning agents advantageous.  

Another object of the present invention is accordingly one for incorporation in detergents and cleaners suitable granules, which enzyme, cyclodextrin, cyclo dextrin derivatives or in the washing or rinsing fluid cyclodextrin or Cyclodextrinderi vate-forming substances, inorganic and / or organic carrier material and ge if necessary contains granulating agent.

Enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof in question. Particularly suitable are from bacterial strains or Fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus and Humicola insolens obtained enzymatic agents. Preferably, proteases are from Subti lisin type and especially proteases derived from Bacillus lentus puts. Enzyme mixtures, for example from protease and amylase or Pro tease and lipase or protease and cellulase or from cellulase and lipase or from Pro tease, amylase and lipase or protease, lipase and cellulase, in particular however Cellulase-containing mixtures of particular interest.

As support materials are in principle all organic or inorganic powdery Substances which are not or only tolerable to the enzymes to be granulated little destroy or deactivate and are stable under granulation conditions. To the Such substances include, for example, starch, cereal flour, cellulose powder, alkali aluminosilicate, in particular zeolite, phyllosilicate, for example bentonite or smectite, and water-soluble inorganic or organic salts, for example alkali metal chloride, alkali metal sulphate, Alkali carbonate or alkali acetate, with sodium or potassium being the preferred alkali metals are. Preference is given to a carrier material mixture of water-swellable starch, cereal demehl and optionally cellulose powder and alkali metal carbonate used.

The water-swellable starch is preferably corn starch, rice starch, potato starch or mixtures thereof, whereby the use of corn starch be is particularly preferred. Swellable starch is in the enzyme granules according to the invention preferably in amounts of 15 to 30 wt .-%. The sum of the quantities is the swellable starch and flour preferably not more than 80% by weight, in particular 32 Wt .-% to 65 wt .-%.  

The cereal flour is in particular a wheat, rye, barley or oatmealable product or a mixture of these flours, wholemeal flours are preferred. Under a wholemeal flour is doing a not fully ground flour understood that has been made from whole, unpeeled grains or at least predominantly consists of such a product, the remainder being fully emollient There is flour or starch. Preferably, commercial wheat flour quality used, such as Type 450 or Type 550. Also, the use of flour products of to the above-mentioned swellable starches leading crops is possible if it care is taken that the flours have been made from whole grains. By the Flour component of the aggregate mixture is known to be an essential Ge achieved odor reduction of the enzyme preparation, which reduces the odor far exceeds the incorporation of equal quantities of corresponding starches. Derar tige cereal flour is preferably in the enzyme granules according to the invention in Men gen of 10 wt .-% to 35 wt .-%, in particular from 15 wt .-% to 25 wt .-% enthal th.

The granules according to the invention can be used as further component of the carrier material preferably 1% by weight to 50% by weight, particularly preferably 5% by weight to 25% by weight, based on the total granules, a Granulierhilfsmittelsystems, the alkali carboxy methylcellulose with degrees of substitution of 0.5 to 1 and polyethylene glycol and / or Alkyl polyethoxylate included. In this granulation auxiliary system are preferably, depending Weil based on finished enzyme granules, 0.5 wt .-% to 5 wt .-% of alkali carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and up to 3 wt .-% polyethylene glycol and / or alkylpolyethoxylate, with particular preference being given to at least 0.5 Wt .-%, in particular 0.8 wt .-% to 2 wt .-% polyethylene glycol with a middle Molar mass below 1000 and / or alkyl polyethoxylate with at least 30 ethoxy groups hand, if more than 2 wt .-% alkali carboxymethylcellulose are included.

Optionally, as additional components of the Granulierhilfsmittelsystems also other cellulose or starch ethers, such as carboxymethyl starch, methyl cellulose, hydroxy ethylcellulose, hydroxypropylcellulose and corresponding cellulose mixed ethers, gelatin, Casein, tragacanth, maltodextrin, sucrose, invert sugar, glucose syrup or others in Water-soluble or readily dispersible oligomers or polymers natural or of synthetic origin. Suitable synthetic water-soluble  Polymers are polyacrylates, polymethacrylates, copolymers of acrylic acid with maleic acid or vinyl group-containing compounds, furthermore polyvinyl alcohol, partially saponified polyvinylacet did and polyvinylpyrrolidone. As far as the aforementioned compounds are such with free carboxyl groups, they are usually in the form of their alkali metal salts, ins particular of their sodium salts, before. Such additional Granulierhilfsmittel can in the Enzyme granules according to the invention in amounts of up to 10 wt .-%, in particular of 0.5 Wt .-% to 8 wt .-% contained. Higher Molecular Weight Polyethylene Glycols, d. H. such with an average molecular weight above 1000, are indeed as synthetic water-soluble Polymers with dust-binding effect useful, but cause the higher molecular weight Polyethylene glycols an undesirable increase in the required granule dissolution time, so that ver preferably to these substances in the enzyme granules according to the invention is canceled.

Another object of the invention is a method for producing a for the one Working in detergents and cleaners suitable enzyme granules, wherein cyclodex trine, cyclodextrin derivatives or in the washing or rinsing liquid cyclodextrin or Cyclodextrin derivatives forming substances, enzymes, inorganic and / or organic Granulated carrier material and optionally excipients in a conventional manner or be agglomerated.

In one possible embodiment, an enzyme granule is prepared by extrusion one by mixing one previously possibly by microfiltration of insoluble Ingredients liberated, concentrated fermentation broth with cyclodextrin, cyclodex trine derivatives or in the washing or rinsing liquid cyclodextrin or cyclodextrin derivatives forming substances and inorganic and / or organic carrier material as Zu precipitate formed, optionally spheronization of the extrudate in a Rondiergerät, drying and applying an outer cladding layer. The Particles preferably have an average particle size of 0.1 mm to 1.4 mm, in particular from 0.5 to 0.8 mm.

In the enzyme granules obtained by this method are cyclodextrin, cyclodextrin derivatives or in the washing or rinsing liquid cyclodextrin or cyclodextrin derivatives bil dende substances evenly with enzyme and other ingredients in the granules ver mixed.  

In another embodiment, the enzyme granules can be obtained by extrusion dieren one by mixing one if necessary previously by microfiltration of insoluble liberated components, concentrated fermentation broth and inorganic and / or organic carrier material as an additive enzyme Vorgemi optionally, spheronization of the extrudate in a rounder, drying and applying an outer coating layer, wherein in a fluidized bed of Extrudate an outer coating layer of a coating system of at least 2% by weight Cyclodextrin, based on the coating layer, cyclodextrin derivatives or in the Washing or rinsing liquid cyclodextrin or cyclodextrin derivatives forming substances applies.

The granules obtained by this process consist of a core and an eu the shell, the core being the enzyme and the outer shell cyclodextrin, cyclodextrin derivatives or in the washing or rinsing liquid cyclodextrin or cyclodextrin derivatives contains forming substances.

A third possible variant of the method provides a combination of the two above The enzyme granules obtained consist of a core and an outer shell with the enzyme in the nucleus and cyclodextrin, cyclodex trine derivatives or in the washing or rinsing liquid cyclodextrin or cyclodextrin derivatives forming substances are contained both in the core and in the envelope.

For the preparation of the enzyme granules according to the invention, preference is given to using Fer ment brewing, for example, by microfiltration of insoluble impurities be be free. The microfiltration is preferably as a cross-flow microfiltration under Use of porous tubes with micropores greater than 0.1 μm, flow rates of Concentrate solution of more than 2 m / s and a pressure difference to the permeate side of performed under 5 bar, such as in the European patent application EP 200 032 described. Subsequently, the microfiltration permeate is preferably by Ultra filtration, optionally followed by vacuum evaporation, concentrated. The Concentration can, as in the international patent application WO 92/11347 be carried out so that only at relatively low levels of Troc kensubstanz of preferably 5 to 50 wt .-%, in particular from 10 wt .-% to 40  % By weight. If protease-containing fermentation broths are used, the Protease content at this stage of the concentrate preferably 500 000 PE / g to 1 500 000 PE / g, in particular 600 000 PE / g to 1 000 000 PE / g. The concentrate becomes a purpose moderately prepared previously dry, powdery to granular mixture of added above aggregates. This mixture also contains, depending on the method of preparation Cyclodextrin, cyclodextrin derivatives or in the washing or rinsing liquid cyclodextrin or cyclodextrin derivatives forming substances. The water content of the mixture should be like this be chosen that it is in the processing with stirring and striking tools in kör transfer non-sticky particles at room temperature and, when using higher Let plastically deform and extrude.

The free-flowing premix obtained is then in principle known manner in a kneader and a connected extruder to a plastic, ho possible processed mass, wherein as a result of mechanical processing, the Mass to temperatures between 40 ° C and 60 ° C, in particular 45 ° C to 55 ° C erwär can. The good leaving the extruder is followed by a perforated disc with led to the beater and thereby to cylindrical particles of defined size crushed. Conveniently, the diameter of the holes in a hole disc 0.7 to 1.6 mm, preferably 0.8 to 1.2 mm. The present in this form Particles can then be dried and coated with a coating system or directly be fed to their later use. However, it has proven to be advantageous then the cylindrical particles leaving the extruder and chopper spheronize, that is to round off and deburr in suitable devices. One can use for this purpose a device consisting of a cylindrical container with stationary, solid side walls and a bottom rotatably mounted friction plate be stands. Devices of this type are under the trade name Marumerizer® in the Technique known and for example in German Auslegeschriften DE 21 37 042 and DE 21 37 043 described. Subsequently, possibly occurring dusty An Parts with a particle size less than 0.1 mm, in particular less than 0.4 mm and any Coarse fractions with a grain size over 2 mm, in particular over 1.6 mm by sieving or Windlasses removed and optionally returned to the manufacturing process. After spheronization, the beads will be continuous or batchwise preferably using a fluidized bed dryer, at supply air temperatures preferably from 35 ° C to 50 ° C and especially at a product temperature of not  above 42 ° C to the desired residual moisture content of, for example, 4 wt .-% to 10 Wt .-%, in particular 5 wt .-% to 8 wt .-%, based on the total granules, ge dries.

After or preferably during drying, additional substances may be used for wrapping and coating the particles are applied. In a preferred embodiment Cyclodextrin, cyclodextrin derivatives or in the washing or rinsing liquid cyclo dextrin or cyclodextrin derivatives forming substances optionally together with applied their suitable envelopes. In this embodiment of the invention Manufacturing process, the coating system as an aqueous solution or dispersion, the preferably from 30% to 65% by weight of water and from 35% to 70% by weight of the over in the coating system, in particular at least 2 wt .-% Cy clodextrin, cyclodextrin derivatives or in the washing or rinsing liquid cyclodextrin or Cyclodextrin derivatives forming substances as well as another component pigment enthal is introduced into the fluidized bed of enzyme-containing cores. Suitable shell sub Punches are in particular the film formers of the aforementioned water-soluble organi polymers. Furthermore, can be at this stage, dyes or pigments Apply to the particles, so any color of their own, most of the Enzymkon centrate, to mask or change. As inert and physiological unbe Thoughtful pigment has proven particularly titanium dioxide, preferably in aq ger dispersion is introduced. The about the dispersion of the coating substances or via an optionally present polymer solution supplied water is in the simultaneously or subsequently again required drying again away.

The enzyme granules of the invention is preferably for the production of solid, esp particular particulate detergent or cleaning agent used by simple Mixing the cyclodextrin, cyclodextrin derivatives or in the washing or rinsing liquid Enzyme granules containing cyclodextrin or cyclodextrin derivatives can be obtained with customary in such agents further powder components. For incorporation into particulate detergents and cleaners, the enzyme gragra preferably has mean particle sizes in the range from 0.1 mm to 2 mm, in particular 0.4 mm to 1.6 mm.  

Through sieving or wind sifting may occur during production dust-like particles with a particle size of less than 0.1 mm, in particular less than 0.4 mm and any coarse fractions with a grain size over 2 mm, in particular over 1.6 mm away and optionally recycled to the manufacturing process. The erfindungsge Granules containing preferably less than 5 wt .-%, in particular at most 1 wt .-% of particles with grain sizes outside the range of 0.2 mm to 1.6 mm.

The enzyme preparation obtained consists of largely rounded, dust-free Parti usually a bulk density of about 500 to 900 grams per liter, in particular from 650 to 880 grams per liter. Your enzyme activity may be due to the flexible drying substance content of the broths before mixing, with the aggregate when using protease-containing fermenter broths to values in the range of preferential Were 150,000 to 350,000 protease units per gram (PE / g), in particular 160,000 PE / g to 300 000 PE / g. The granules according to the invention are characterized by a very high storage stability, especially at temperatures above Raumtem temperature and high humidity, as well as a rapid solution behavior in the wash liquor out. Preferably, the granules of the invention set 100% of their enzyme activity within 3 minutes, especially within 90 seconds to 2 minutes, in Water free at 25 ° C.

Examples

The inhibition of color transfer was examined.

Examples 1 to 3

White cotton lobes were placed in a pre-washed wash liquor containing 0.5 g / l han commercial detergent (Persil® supra, manufacturer Henkel kGaA, Dusseldorf) and 2 wt .-%, based on the detergent, γ-cyclodextrin contained immersed. It became a solution of Congo Red (manufacturer Sigma C-6767) in an amount of 14.6 mg Congo red / l wash liquor added. The solution was incubated for 40 min. At 40 ° C. Subsequently were the fabrics are well rinsed, dried, ironed.

Comparative example

As a comparison, white cotton lobes were as described in Example 1 be with the exception that the wash liquor does not contain non-enzymatic proteins and / or protein hydrolysates.

The remission of the dried tissue was achieved with a Dr. med. Long colorimeter measured. The following values were determined:

remission example 1 41.1 Example 2 40.1 Example 3 41.0 Comparative example 38.3

From the examples it is clear that the addition of cyclodextrins, cyclodextrin derivatives or forming cyclodextrin or cyclodextrin derivatives in the wash or rinse liquid Substances to a dye-containing wash liquor to a much lower Verfär exercise of the tissue leads.

Claims (13)

1. A method for inhibiting the color transfer of dyed textiles to other textiles during washing or rinsing in a washing or rinsing liquid, characterized in that the washing or rinsing liquid cyclodextrin, Cy clodextrinderivate or in the washing or rinsing liquid cyclodextrin or cyclo dextrin derivatives forming Substances are added. 2. The method according to claim 1, characterized in that the cyclodextrins, Cyclodextrin derivatives or in the washing or rinsing liquid cyclodextrin or Cyclodextrin derivatives forming substances in an amount of 0.1 to 5.0 wt .-%, based on the weight of the textiles to be cleaned or rinsed. 3. The method according to any one of claims 1 to 2, characterized in that one Add the substances at the beginning or during the washing or rinsing process. 4. Enzyme granules suitable for incorporation in detergents and cleaners containing enzyme, cyclodextrin, cyclodextrin derivatives or in the washing or Rinsing fluid cyclodextrin or cyclodextrin derivatives forming substances and on organic and / or organic carrier material and optionally granulation tool. 5. Granules according to claim 4, characterized in that it is enzyme from the class containing proteases, lipases, amylases, cellulases or mixtures thereof. 6. Granules according to one of claims 4 or 5, characterized in that it Cy clodextrine, cyclodextrin derivatives or in the washing or rinsing liquid cyclo dextrin or cyclodextrin derivatives forming substances in an amount of 0.1 to 5.0 wt .-%, based on the weight of the granules contains. 7. A process for the preparation of a for incorporation in washing and Reinigungsmit suitable enzyme granules, characterized in that cyclodextrins, Cy clodextrin derivatives or those in the washing or rinsing liquid cyclodextrin or Cyclodextrin derivatives forming substances, enzymes, inorganic and / or or  ganic carrier material and optionally excipients in per se known Granulated or agglomerated. 8. The method according to claim 7, characterized in that a by mixing of cyclodextrins, cyclodextrin derivatives or in the washing or rinsing liquid Cyclodextrin or cyclodextrin derivatives forming substances and anorgani Shem and / or organic support material as additive ago extruded extruded, optionally in a Rondiergerät is spheronised and dried. 9. The method according to any one of claims 7 or 8, characterized in that a outer cladding layer is applied. 10. The method according to any one of claims 7 to 9, characterized in that the Premix an optionally previously by microfiltration of insoluble Be freed, concentrated fermentation broth is added. 11. A process for the preparation of a for incorporation in washing and Reinigungsmit a suitable particle by extruding one by mixing a given previously freed from insoluble components by microfiltration, aufkon centered fermentation broth and inorganic and / or organic carrier material produced as an additive enzyme premix, optionally Spheronization of the extrudate in a rounder, drying and application an outer coating layer, wherein in a fluidized bed of extrudate an outer coating layer, the cyclodextrins, cyclodextrin derivatives or in the washing or rinsing liquid cyclodextrin or cyclodextrin derivatives contains forming substances. 12. The method according to claim 11, characterized in that the coating system as an aqueous solution or dispersion, which is preferably 30% by weight to 65% by weight Water and 35% to 70% by weight of the coating system to which En zym-containing cores is applied, wherein in the coating system at least 2  % By weight of cyclodextrins, cyclodextrin derivatives or those in the wash or rinse liquid cyclodextrin or cyclodextrin derivatives forming substances and up to 20 Wt .-% nonionic surfactants, polyethylene glycol, waxes, pigments, etc. included are. 13. Use of an enzyme granulate according to any one of claims 4 to 6 for the manufacture tion of solid, in particular particulate detergent.