Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3937—Stabilising agents
  • C11D3/394—Organic compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives

Definitions

• the invention relates to new, biodegradable stabilizers for textile bleaching systems in the presence of heavy metal traces based on proteins and / or protein secondary products.
• sodium perborate, sodium percarbonate and hydrogen peroxide are almost exclusively used as bleaches for textile bleaching during washing, which, in addition to the surfactants and other active ingredients, are said to contribute to dirt detachment and fabric lightening during the washing process (see, for example, Jakobi Lschreib, Detergents and Textile Washing, VCH 1987 ).
• Typical stains that can hardly be removed without bleaching agents include, for example, red and blue anthocyanin dyes from the fruit, curcuma dye from curry and mustard, brown tannins from tea, humic acids from coffee, tea, cocoa and carotenoid dyes from carrots and tomatoes.
• the principal mode of action of the bleaching agents comprises the chemical saturation of delocalized double bond systems of the colored soils by hydroxylation and their subsequent oxidative fragmentation to form water-soluble products.
• a high effectiveness of the bleaching presupposes an oxidative attack on the double bonds of the colored soiling which is as selective as possible in order to protect the textile fibers present in large excess against oxidative damage.
• the sodium perborate is in the crystalline state as a defined peroxodiborate ion, and therefore shows extremely good storage stability even when mixed with a detergent powder.
• the percarbonate on the other hand, crystallizes as a real peroxohydrate and is already unstable to atmospheric moisture and cannot be mixed with other detergent ingredients. It is mainly used as bleaching salt and in multi-component detergents, where it can be stored separately from the detergents.
• the hydrogen peroxide bleaching mechanism can be ionic as well as radical. However, the ionic alone is optimal while protecting the laundry. Hydrogen peroxide undergoes heterolytic cleavage in an alkaline medium into a perhydroxyl anion, which is the actual selective bleaching species: H2O2 ⁇ HOO ⁇ + H+
• TAED tetraacetylethylenediamine
• the chemical bonds of the textile fibers are also attacked, which can lead to severe textile damage and even pitting.
• the homolysis of hydrogen peroxide is catalyzed by heavy metal ions.
• the unavoidable traces of heavy metals can make homolysis the main reaction and the bleaching effect is significantly weakened.
• the homolysis can be largely suppressed by masking the heavy metal ions.
• DE-OS 703 604 describes a process for stabilizing per compounds during textile washing by magnesium silicate.
• all detergents today contain magnesium silicate. However, its effect is not enough.
• the stabilizing effect is enhanced by combination with a strong complexing agent such as ethylenediaminetetraacetate (EDTA) or phosphonates such as diethylenetriaminepentamethylenephosphonate (DTPMP).
• EDTA ethylenediaminetetraacetate
• DTPMP diethylenetriaminepentamethylenephosphonate
• the stabilizing effect described above by adding complexing agents in textile bleaching is positively due to the fact that the drinking water in particular contains only a very low Fe content.
• the guideline for drinking water [Ullmann Encyclopedia of Technical Chemistry, Vol. 24, p. 187 (4th edition, 1983)] is 50 ⁇ g / l Fe, but 0.1 - 3.0 mg / l Cu.
• the low Fe concentration has no significant influence on the hydrogen peroxide bleaching, however, a noticeable H2O2 decomposition occurs at a Cu content of 0.1 ppm Cu. At a content of 0.6 ppm Cu, decomposition occurs spontaneously and the bleaching effect is lost.
• the manganese content is also max.
• Bleach stabilizers are contained in the usual detergent frame formulations in amounts of 0.1-2%.
• complex copper ions are e.g. B. tartaric acid and amino acids.
• the complexes are deep blue in water soluble and resistant to alkali. However, their stability is not sufficient to prevent the radical decomposition of hydrogen peroxide in the presence of copper ions.
• the proteins and / or protein secondary products according to the invention form copper complexes which are so stable that they are resistant to alkali with simultaneous stabilization of H2O2 solutions. Furthermore, it was surprisingly found that when washing a tea-soiled cotton fabric with a common detergent formulation, the addition of protein or protein secondary products in the presence of copper and iron ions results in a significantly better soil detachment than without addition.
• the protein bodies to be used according to the invention can be isolated, for example, enzymatically or by acid hydrolysis from the organic raw materials collagen, casein or keratin and from yeast residues, which are often obtained in large quantities as waste products.
• the proteins or protein secondary products used should have an average molecular weight of 500 to 100,000, preferably 500 to 5,000.
• Particularly preferred feedstocks are collagen hydrolyzates, chemically modified collagen protein hydrolyzates also being used, of which carboxylmethylated collagen protein hydrolyzates are particularly preferred.
• All previously known complexing agents for textile bleaching form copper complexes with oxygen or mixed oxygen-nitrogen ligands (e.g. EDTA and DTPMP).
• oxygen or mixed oxygen-nitrogen ligands e.g. EDTA and DTPMP.
• proteins are effective as stabilizers for textile bleaching systems in the presence of copper and iron, which are present in concentrations as would be expected for normal textile washing.
• the protein substances in addition to their biological origin and their degradability, have the further advantage that they are resistant to oxidation against hydrogen peroxide.
• a collagen-based protein hydrolyzate produced by enzymatic means was used in the examples:
• the active oxygen specified in the following examples was determined using the following method: Hydrogen peroxide reacts in acidic solution as follows: H2O2 + 2 J ⁇ + 2 H+ ⁇ J2 + 2 H2O
• 50 ml of the product solution to be determined are pipetted off and immediately added to a solution of 50 ml of isopropanol, 25 ml of potassium iodide solution (33.2 g / l, saturated) and 10 ml of 10% by weight sulfuric acid. This solution is heated under reflux for 2 minutes, the condenser is rinsed thoroughly with isopropanol and titrated against colorless with 0.1 N sodium thiosulfate solution. 1 ml 0.1 Na2S2O3 solution ⁇ 0.05 mmol hydrogen peroxide
• the copper ions and the protein hydrolyzate are placed in 1 liter of deionized water at 60 ° C.
• the amount of sodium perborate is added as a powder just before the measurement.
• Example 1 shows that in the presence of only 0.64 mg / l copper ions, the perborate solution is completely decomposed after only 5 minutes, while complete stabilization is achieved by adding 0.3 g of protein hydrolyzate to the copper solution: after 3 97.9% of active oxygen is still available for hours.
• the decrease in active oxygen in the solution is determined as a function of time:
• Carboxymethylated protein hydrolyzate shows approximately the same stabilizing effect on copper-containing perborate solutions as the protein hydrolyzate mentioned in Example 1.
• Example 2 The test is carried out analogously to Example 1. Instead of copper ions, iron ions are introduced. Ethylene diamine tetraacetate (EDTA) serves as the reference substance.
• EDTA Ethylene diamine tetraacetate
• iron ions In low concentrations of 0.6 ppm, iron ions have no influence on the stability of perborate solutions. The addition of protein shows no impairment. In contrast, the addition of EDTA accelerates the decomposition of iron-containing perborate solutions, which means a worse effect.
• Oxidation stability of protein hydrolyzate (Prot.) Against sodium perborate solutions with the exclusion of heavy metals.
• Ethylamine tetraacetate is used as the reference substance. Protein is not oxidatively attacked by perborate solutions. EDTA, on the other hand, is oxidized by perborate.
• This example shows the stabilization of the bleach in a conventional detergent formulation in the presence of copper and iron ions by adding protein hydrolyzate (Prot.) Or carboxymethylated protein hydrolyzate.
• test fabric is washed in 250 ml of washing liquor at 60 ° C. for 30 minutes, then rinsed and dried.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)

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Cited By (9)

Citations (3)

• 1991
  • 1991-04-20 DE DE4113003A patent/DE4113003A1/de not_active Withdrawn
• 1992
  • 1992-02-28 EP EP92103429A patent/EP0510331A1/fr not_active Withdrawn
  • 1992-04-17 JP JP4098266A patent/JPH0657626A/ja not_active Withdrawn

Patent Citations (3)

Non-Patent Citations (1)

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