EP0510331A1 - Protéine comme stabilisateur biodégradable pour le blanchiment à l'oxygène utilisé dans le lavage du linge - Google Patents

Protéine comme stabilisateur biodégradable pour le blanchiment à l'oxygène utilisé dans le lavage du linge Download PDF

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Publication number
EP0510331A1
EP0510331A1 EP92103429A EP92103429A EP0510331A1 EP 0510331 A1 EP0510331 A1 EP 0510331A1 EP 92103429 A EP92103429 A EP 92103429A EP 92103429 A EP92103429 A EP 92103429A EP 0510331 A1 EP0510331 A1 EP 0510331A1
Authority
EP
European Patent Office
Prior art keywords
protein
bleach
bleaching
prot
collagen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP92103429A
Other languages
German (de)
English (en)
Inventor
Heike Dr. Kelkenberg
Harald Dr. Lüders
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huels AG
Original Assignee
Huels AG
Chemische Werke Huels AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huels AG, Chemische Werke Huels AG filed Critical Huels AG
Publication of EP0510331A1 publication Critical patent/EP0510331A1/fr
Withdrawn legal-status Critical Current

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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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (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)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
EP92103429A 1991-04-20 1992-02-28 Protéine comme stabilisateur biodégradable pour le blanchiment à l'oxygène utilisé dans le lavage du linge Withdrawn EP0510331A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4113003A DE4113003A1 (de) 1991-04-20 1991-04-20 Eiweiss als bioabbaubarer stabilisator fuer die sauerstoffbleiche der textilwaesche
DE4113003 1991-04-20

Publications (1)

Publication Number Publication Date
EP0510331A1 true EP0510331A1 (fr) 1992-10-28

Family

ID=6430048

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92103429A Withdrawn EP0510331A1 (fr) 1991-04-20 1992-02-28 Protéine comme stabilisateur biodégradable pour le blanchiment à l'oxygène utilisé dans le lavage du linge

Country Status (3)

Country Link
EP (1) EP0510331A1 (fr)
JP (1) JPH0657626A (fr)
DE (1) DE4113003A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0690122A2 (fr) 1994-06-30 1996-01-03 The Procter & Gamble Company Compositions détergentes
US5760150A (en) * 1993-12-23 1998-06-02 Th. Goldschmidt Ag Copolymerizates of unsaturated carboxylic acids, process for the preparation thereof and use thereof
WO1999026508A1 (fr) 1997-11-21 1999-06-03 The Procter & Gamble Company Applicateur de produit
WO2002040370A1 (fr) 2000-11-17 2002-05-23 The Procter & Gamble Company Sachets solubles dans l'eau
WO2006068306A2 (fr) 2004-12-22 2006-06-29 Fujifilm Corporation Composition de sterilisation contenant un acide o-alkoxyperoxy carboxylique
WO2010084351A1 (fr) 2009-01-26 2010-07-29 Innospec Limited Agents chélatants et procédés liés à ceux-ci
WO2015191343A1 (fr) 2014-06-12 2015-12-17 The Procter & Gamble Company Système et procédés de détection et de mise en évidence d'un endommagement de cheveux par ultraviolets par l'intermédiaire de l'évaluation de fragments de protéine
IT201700016547A1 (it) * 2017-02-15 2018-08-15 Lamberti Spa Fertilizzanti
WO2024126730A1 (fr) 2022-12-16 2024-06-20 Innospec Performance Chemicals Italia Srl Compositions particulaires
WO2026008699A2 (fr) 2024-07-02 2026-01-08 Innospec Limited Compositions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DOP2019000173A (es) 2019-06-21 2019-09-30 Maria Portillo Rosado Rosa Composicion limpiadora multiusos a base de colageno.

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3107260A (en) * 1960-11-29 1963-10-15 Geigy Chem Corp Triaminopropane hexa-acetic acid and metal chelates thereof
GB1383741A (en) * 1971-04-13 1974-02-12 Ciba Geigy Ag Stabilisation of per-compounds
EP0396999A2 (fr) * 1989-05-06 1990-11-14 BASF Aktiengesellschaft Acides 2-méthyl et 2-hydroxyméthyl-sérine-N,N-diacétiques et leurs dérivés

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3107260A (en) * 1960-11-29 1963-10-15 Geigy Chem Corp Triaminopropane hexa-acetic acid and metal chelates thereof
GB1383741A (en) * 1971-04-13 1974-02-12 Ciba Geigy Ag Stabilisation of per-compounds
EP0396999A2 (fr) * 1989-05-06 1990-11-14 BASF Aktiengesellschaft Acides 2-méthyl et 2-hydroxyméthyl-sérine-N,N-diacétiques et leurs dérivés

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
'Gmelins Handbuch der Anorganischen Chemie, 8. Auflage, "Kupfer" Teil B-Lieferung 4' 1966 , VERLAG CHEMIE GMBH , WEINHEIM *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5760150A (en) * 1993-12-23 1998-06-02 Th. Goldschmidt Ag Copolymerizates of unsaturated carboxylic acids, process for the preparation thereof and use thereof
EP0690122A2 (fr) 1994-06-30 1996-01-03 The Procter & Gamble Company Compositions détergentes
WO1999026508A1 (fr) 1997-11-21 1999-06-03 The Procter & Gamble Company Applicateur de produit
WO2002040370A1 (fr) 2000-11-17 2002-05-23 The Procter & Gamble Company Sachets solubles dans l'eau
WO2006068306A2 (fr) 2004-12-22 2006-06-29 Fujifilm Corporation Composition de sterilisation contenant un acide o-alkoxyperoxy carboxylique
WO2010084351A1 (fr) 2009-01-26 2010-07-29 Innospec Limited Agents chélatants et procédés liés à ceux-ci
WO2015191343A1 (fr) 2014-06-12 2015-12-17 The Procter & Gamble Company Système et procédés de détection et de mise en évidence d'un endommagement de cheveux par ultraviolets par l'intermédiaire de l'évaluation de fragments de protéine
IT201700016547A1 (it) * 2017-02-15 2018-08-15 Lamberti Spa Fertilizzanti
WO2018149773A1 (fr) * 2017-02-15 2018-08-23 Lamberti Spa Engrais
WO2024126730A1 (fr) 2022-12-16 2024-06-20 Innospec Performance Chemicals Italia Srl Compositions particulaires
WO2026008699A2 (fr) 2024-07-02 2026-01-08 Innospec Limited Compositions

Also Published As

Publication number Publication date
JPH0657626A (ja) 1994-03-01
DE4113003A1 (de) 1992-10-22

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