EP0641379A1 - Process for stabilizing the colour of surfactants - Google Patents

Process for stabilizing the colour of surfactants

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Publication number
EP0641379A1
EP0641379A1 EP93912702A EP93912702A EP0641379A1 EP 0641379 A1 EP0641379 A1 EP 0641379A1 EP 93912702 A EP93912702 A EP 93912702A EP 93912702 A EP93912702 A EP 93912702A EP 0641379 A1 EP0641379 A1 EP 0641379A1
Authority
EP
European Patent Office
Prior art keywords
sulfates
surfactants
ether
alkyl
group
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.)
Ceased
Application number
EP93912702A
Other languages
German (de)
French (fr)
Inventor
Helmut Blum
Siglinde Erpenbach
Hermann Hensen
Werner Seipel
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0641379A1 publication Critical patent/EP0641379A1/en
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/51—Chelating agents

Definitions

  • the invention relates to a method for color stabilization of surfactants, in which selected inhibitors are added.
  • Surfactants such as fatty alcohol ether sulfates are used, among other things, for the production of washing. Dishwashing and cleaning agents as well as hair and body care products. If these products come onto the market as raw materials, they are usually adjusted to a pH of 7 to 9 by adding alkalis before further use. As a result of the manufacturing process, e.g. B. the sulfonation with chlorosulfonic acid, which always contains traces of iron, as well as contamination during transport and storage, such surfactants always have a low iron ion content. Since these act as autoxidation promoters, iron contamination leads to the formation of undesirable and often color-causing oxidation products. At higher pH values, a fine colloidal precipitation of iron (III) - come hydroxide, which makes further processing of the surfactants into final formulations difficult, if not impossible.
  • the object of the invention was therefore to develop new stabilizers for surfactants which are free from the disadvantages described.
  • the invention relates to a method for stabilizing surfactants, in which inhibitors of the formula (I) are added,
  • Rl and R3 are independently hydrogen or one
  • inhibitors mentioned stabilizes anionic, nonionic and / or amphoteric or zwitterioic surfactants reliably and permanently against discoloration.
  • a particular advantage of the inhibitors to be used according to the invention is their excellent biodegradability.
  • Suitable surfactants are aqueous, anionic, nonionic and / or amphoteric or zwitterionic surfactants, which can be in the form of solutions or pastes.
  • anionic surfactants which can be stabilized in the sense of the process according to the invention are alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, o-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, hydroxyl ether sulfates, glycerol ether sulfates ) sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, Sulfosuccinamates, sulfotriglycerides, ether carboxylic acids, alkyl oligoglucoside sulfates and alkyl (ether) phosphates.
  • nonionic surfactants which can be stabilized by the process according to the invention are fatty alcohol ethoxylates, polyol fatty acid esters, alkyl oligoglycosides, sorbitan esters and polysorbates, while amphoteric or zwitterionic surfactants are, for example, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobins.
  • the surfactants can have a solids content of 5 to 85, preferably 25 to 70% by weight, based on the products.
  • inhibitors which are suitable for stabilizing surfactants in the sense of the process according to the invention are N- (carboxymethyl) aminosuccinic acid, N- (1,2-dicarboxyethyl) aspartic acid, nitrilodiacetic acid-3-propionic acid, glucamine-N, N-diacetic acid, hydroxyethyliminodi- H 0204/0205 - 5 -
  • acetic acid and in particular N- (1,2-dicarboxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid, isoserine-N, N-diacetic acid and nitrilotriacetic acid.
  • N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid can be prepared by ring opening epoxysuccinic acid with aspartic acid or nitrilodiacetic acid-3-propionic acid by reacting iminodiacetic acid with acrylic acid [DE-A-40 24 552, Henkel] .
  • the inhibitors can be added to the surfactants in amounts of 10 to 1500, preferably 100 to 500 ppm, based on the solids content of the products. Furthermore, it has proven to be particularly advantageous to adjust the surfactants to a pH of 7 to 11, preferably 7.5 to 9.
  • the surfactants obtainable by the process according to the invention are stabilized against discoloration and are suitable for the production of detergents, dishwashing detergents and cleaning agents and products for hair and body care, in which they are present in amounts of 1 to 90, preferably 5 to 50 % By weight, based on the composition, may be present.
  • NTA Nitrilotriacetic acid
  • Ci2 / 14- ⁇ ° kosfettalkohol-2EO ether sulfate Na salt (Texapon ( R ), 26.5 wt .-% in water, Henkel KGaA, Dusseldorf, FRG) was with a content of 10 ppm Iron (in the form of iron (III) chloride) and optionally 150 ppm inhibitor - in each case based on the solids content of the products - added.
  • the ether sulfate known from Examples 1 to 9 was doped with 40 ppm iron and 150 ppm inhibitor - in each case based on the solids content of the products - and over a period of 21 d at pH values in the range from 8 to 11 as previously described stored.
  • the color numbers are shown in Tab. 3.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Surfactants may be stabilized against discolouring by adding thereto an inhibitor having the formula (I), in which R?1 and R?3 represent independently from each other hydrogen or a carboxyl group; R?2 stands for hydrogen or a CH2?COOH group; R?4 stands for a carboxyl, hydroxyl, CH(OH)COOH or (CHOH)5?H group and n and m are 0 or 1 independently from each other.

Description

Verfahren zur Farbstabilisierung von Tensiden Process for color stabilization of surfactants
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft ein Verfahren zur Farbstabilisierung von Tensiden, bei dem man ihnen ausgesuchte Inhibitoren zu¬ setzt.The invention relates to a method for color stabilization of surfactants, in which selected inhibitors are added.
Stand der TechnikState of the art
Tenside, wie beispielsweise Fettalkoholethersulfate dienen u.a. zur Herstellung von wasch-. Spül- und Reinigungsmitteln sowie Produkten der Haar- und Körperpflege. Kommen diese Produkte als Rohstoffe in den Handel, werden sie vor einer weiteren Verwendung üblicherweise durch Zusatz von Alkalien auf einen pH-Wert von 7 bis 9 eingestellt. Als Folge der Herstellungsverfahren, z. B. der Sulfierung mit Chlorsulfon- säure, die stets Spuren von Eisen enthält, sowie durch Kon¬ tamination während Transport und Lagerung, weisen derartige Tenside stets einen geringen Gehalt an Eisenionen auf. Da diese als Autoxidationspromotoren wirken, führt eine Eisen¬ belastung zur Bildung unerwünschter und häufig farbverur- sachender Oxidationsprodukte. Bei höheren pH-Werten kann es ferner zu einer fein-kolloidalen Ausfällung von Eisen-(III)- hydroxid kommen, die eine Weiterverarbeitung der Tenside hin zu Endformulierungen erschwert, wenn nicht gar unmöglich macht.Surfactants such as fatty alcohol ether sulfates are used, among other things, for the production of washing. Dishwashing and cleaning agents as well as hair and body care products. If these products come onto the market as raw materials, they are usually adjusted to a pH of 7 to 9 by adding alkalis before further use. As a result of the manufacturing process, e.g. B. the sulfonation with chlorosulfonic acid, which always contains traces of iron, as well as contamination during transport and storage, such surfactants always have a low iron ion content. Since these act as autoxidation promoters, iron contamination leads to the formation of undesirable and often color-causing oxidation products. At higher pH values, a fine colloidal precipitation of iron (III) - come hydroxide, which makes further processing of the surfactants into final formulations difficult, if not impossible.
In der Vergangenheit hat es nicht an Versuchen gemangelt, Tenside gegenüber Verfärbungen zu stabilisieren. Es hat sich jedoch erwiesen, daß übliche Komplexierungs- bzw. Chelati- sierungsmittel für Eisenionen nicht den gewünschten Erfolg zeigen. Als einen potentiell wirksamen Inhibitor wurde zwar Ethylendiamintetraessigsäure (EDTA) gefunden, infolge der nicht zufriedenstellenden biologischen Endabbaubarkeit kommt der Einsatz dieses Stoffes jedoch nur eingeschränkt in Be¬ tracht.There has been no shortage of attempts in the past to stabilize surfactants against discoloration. However, it has been found that conventional complexing or chelating agents for iron ions do not show the desired success. Although ethylenediaminetetraacetic acid (EDTA) has been found as a potentially effective inhibitor, the use of this substance is only of limited use owing to the unsatisfactory biodegradability.
Die Aufgabe der Erfindung bestand somit darin, neue Stabili¬ satoren für Tenside zu entwickeln, die frei von den geschil¬ derten Nachteilen sind.The object of the invention was therefore to develop new stabilizers for surfactants which are free from the disadvantages described.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung ist ein Verfahren zur Stabilisierung von Tensiden, bei dem man ihnen Inhibitoren der Formel (I) zusetzt,The invention relates to a method for stabilizing surfactants, in which inhibitors of the formula (I) are added,
R1 R3 R 1 R 3
I II I
HOOC-(CH2)n-CH-N-CH-(CH2)m-R4 __ t1)HOOC- (CH2) n -CH-N-CH- (CH2) m -R 4 __ t 1 )
I R2 in derI R2 in the
Rl und R3 unabhängig voneinander für Wasserstoff oder eineRl and R3 are independently hydrogen or one
Carboxylgruppe, R2 für Wasserstoff oder eine CH2C00H-Gruppe, R4 für eine Carboxyl-, Hydroxyl-, CH(OH)COOH- oderCarboxyl group, R2 for hydrogen or a CH2C00H group, R 4 for a carboxyl, hydroxyl, CH (OH) COOH or
(CH0H)5H-Gruppe sowie n und m unabhängig für 0 oder 1(CH0H) 5H group and n and m independently for 0 or 1
steht.stands.
Überraschenderweise wurde gefunden, daß schon der Zusatz kleiner Mengen der genannten Inhibitoren anionische, nicht¬ ionische und/oder amphotere bzw. zwitteriohische Tenside zu¬ verlässig und dauerhaft gegenüber Verfärbungen stabilisiert. Ein besonderer Vorteil der erfindungsgemäß einzusetzenden Inhibitoren besteht dabei in ihrer ausgezeichneten biolo¬ gischen Endabbaubarkeit.Surprisingly, it has been found that the addition of small amounts of the inhibitors mentioned stabilizes anionic, nonionic and / or amphoteric or zwitterioic surfactants reliably and permanently against discoloration. A particular advantage of the inhibitors to be used according to the invention is their excellent biodegradability.
Als Tenside kommen wäßrige, anionische, nichtionische und/oder amphotere bzw. zwitterionische Tenside in Betracht, die in Form von Lösungen oder Pasten vorliegen können.Suitable surfactants are aqueous, anionic, nonionic and / or amphoteric or zwitterionic surfactants, which can be in the form of solutions or pastes.
Typische Beispiele anionischer Tenside, die im Sinne des er¬ findungsgemäßen Verfahrens stabilisiert werden können, sind Alkylbenzolsulfonate, Alkansulfonate, Olefinsulfonate, Alkyl- ethersulfonate, Glycerinethersulfonate, oe-Methylestersulfona¬ te, Sulfofettsäuren, Alkylsulfate, Fettalkoholethersulfate, Glycerinethersulfate, Hydroxymischethersulfate, Monoglycerid- (ether)sulfate, Fettsäureamid(ether)sulfate, Sulfosuccinate, Sulfosuccinamate, Sulfotriglyceride, Ethercarbonsäuren, Al- kyloligoglucosidsulfate und Alkyl(ether)phosphate.Typical examples of anionic surfactants which can be stabilized in the sense of the process according to the invention are alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, o-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, hydroxyl ether sulfates, glycerol ether sulfates ) sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, Sulfosuccinamates, sulfotriglycerides, ether carboxylic acids, alkyl oligoglucoside sulfates and alkyl (ether) phosphates.
Beispiele für nichtionische Tenside, die nach dem erfindungs- gemäßen Verfahren stabilisiert werden können, sind Fettalko- holethoxylate, Polyolfettsäureester, Alkyloligoglycoside , Sorbitanester und Polysorbate, während als amphotere bzw. zwitterionische Tenside beispielsweise Alkylamidobetaine, Aminopropionate, Aminoglycinate, Imidazoliniumbetaine und Sulfobetaine in Betracht kommen.Examples of nonionic surfactants which can be stabilized by the process according to the invention are fatty alcohol ethoxylates, polyol fatty acid esters, alkyl oligoglycosides, sorbitan esters and polysorbates, while amphoteric or zwitterionic surfactants are, for example, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobins.
Bei allen genannten Tensiden handelt es sich um bekannte Stoffe, die nach den einschlägigen Methoden der praparativen organischen Chemie hergestellt werden können. In diesem Zu¬ sammenhang sei auf entsprechende Übersichtsarbeiten, bei¬ spielsweise J. Falbe (ed) "Surfactants in consumer pro- ducts", Springer Verlag, 1987, S.54. - 124 oder J. Falbe (ed) "Katalysatoren, Tenside, Schmiermittelπ, Thieme Verlag, 1978, S.126-149 verwiesen.All of the surfactants mentioned are known substances which can be prepared by the relevant methods of preparative organic chemistry. In this context, reference is made to corresponding reviews, for example J. Falbe (ed) "Surfactants in consumer products", Springer Verlag, 1987, p. 54. - 124 or J. Falbe (ed) "Catalysts, surfactants, lubricants π , Thieme Verlag, 1978, p.126-149 referenced.
Im Sinne des erfindungsgemäßen Verfahrens hat sich die Sta¬ bilisierung von wäßrigen Alkylsulfaten bzw. Fettalkohol- ethersulfaten als besonders wirksam erwiesen. Die Tenside können dabei einen Feststoffgehalt von 5 bis 85, vorzugsweise 25 bis 70 Gew.-% - bezogen auf die Produkte - aufweisen.In the sense of the method according to the invention, the stabilization of aqueous alkyl sulfates or fatty alcohol ether sulfates has proven to be particularly effective. The surfactants can have a solids content of 5 to 85, preferably 25 to 70% by weight, based on the products.
Typische Beispiele für Inhibitoren, die im Sinne des erfin¬ dungsgemäßen Verfahrens zur Stabilisierung von Tensiden in Betracht kommen, sind N-(Carboxymethyl)aminobernsteinsäure, N-(1,2-Dicarboxyethyl)asparaginsäure, Nitrilodiessigsäure-3- propionsäure, Glucamin-N,N-diessigsäure, Hydroxyethyliminodi- H 0204/0205 - 5 -Typical examples of inhibitors which are suitable for stabilizing surfactants in the sense of the process according to the invention are N- (carboxymethyl) aminosuccinic acid, N- (1,2-dicarboxyethyl) aspartic acid, nitrilodiacetic acid-3-propionic acid, glucamine-N, N-diacetic acid, hydroxyethyliminodi- H 0204/0205 - 5 -
essigsaure sowie insbesondere N-(l,2-Dicarboxyethyl)glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)asparaginsäure, Isoserin- N,N-diessigsäure und Nitrilotriessigsäure.acetic acid and in particular N- (1,2-dicarboxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid, isoserine-N, N-diacetic acid and nitrilotriacetic acid.
Bei den Inhibitoren der Formel (I) handelt es sich ebenfalls um bekannte Stoffe, die nach einschlägigen Verfahren der pra¬ parativen organischen Chemie erhältlich sind. So kann bei¬ spielsweise N-(1,2-Dicarboxy-2-hydroxyethyl)asparaginsäure durch Ringöffnung von Epoxybernsteinsäure mit Asparaginsäure oder Nitrilodiessigsäure-3-propionsäure durch Umsetzung von Iminodiessigsäure mit Acrylsäure hergestellt werden [DE-A-40 24 552, Henkel]. Zur Herstellung von N-(Caboxymethyl)amino- bernsteinsäure sei auf die Offenlegungsschrift DE-A-22 20 295 (Unilever), zur Herstellung von N-(l,2-Dicarboxy-2-hydroxy- ethyl)-glycin auf die Offenlegungsschrift DE-A-22 41 134 (Hoechst) verwiesen.The inhibitors of the formula (I) are likewise known substances which can be obtained by relevant processes in preparative organic chemistry. For example, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid can be prepared by ring opening epoxysuccinic acid with aspartic acid or nitrilodiacetic acid-3-propionic acid by reacting iminodiacetic acid with acrylic acid [DE-A-40 24 552, Henkel] . For the production of N- (caboxymethyl) aminosuccinic acid, reference is made to the published patent application DE-A-22 20 295 (Unilever), and for the production of N- (1,2-dicarboxy-2-hydroxyethyl) glycine to the published patent application DE -A-22 41 134 (Hoechst).
Die Inhibitoren können den Tensiden in Mengen von 10 bis 1500, vorzugsweise 100 bis 500 ppm - bezogen auf den Fest¬ stoffgehalt der Produkte - zugesetzt werden. Des weiteren hat es sich als besonders vorteilhaft erwiesen, die Tenside auf einen pH-Wert von 7 bis 11, vorzugsweise 7,5 bis 9 einzu¬ stellen. The inhibitors can be added to the surfactants in amounts of 10 to 1500, preferably 100 to 500 ppm, based on the solids content of the products. Furthermore, it has proven to be particularly advantageous to adjust the surfactants to a pH of 7 to 11, preferably 7.5 to 9.
Gewerbliche AnwendbarkeitIndustrial applicability
Die nach dem erfindungsgemäßen Verfahren erhältlichen Tenside sind gegen Verfärbung stabilisiert und eignen sich zur Her¬ stellung von Wasch-, Spül- und Reinigungsmitteln sowie Pro¬ dukten zur Haar- und Körperpflege, in denen sie in Mengen von 1 bis 90, vorzugsweise 5 bis 50 Gew.-% - bezogen auf die Mittel - enthalten sein können.The surfactants obtainable by the process according to the invention are stabilized against discoloration and are suitable for the production of detergents, dishwashing detergents and cleaning agents and products for hair and body care, in which they are present in amounts of 1 to 90, preferably 5 to 50 % By weight, based on the composition, may be present.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. The following examples are intended to explain the subject matter of the invention in more detail without restricting it.
BeispieleExamples
I) Erfindungsgemäße InhibitorenI) Inhibitors according to the invention
R1 R3 R 1 R 3
I II I
HOOC-(CH2)n-CH-N-CH-(CH2)m-R4 (I)HOOC- (CH 2 ) n -CH-N-CH- (CH2) m -R 4 (I)
I R2I R2
1) N-(Carboxymethyl)aminobernsteinsäure1) N- (Carboxymethyl) aminosuccinic acid
2) N-(1,2-Dicarboxyethyl)-asparaginsäure2) N- (1,2-dicarboxyethyl) aspartic acid
3) N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin3) N- (1,2-dicarboxy-2-hydroxyethyl) glycine
4) N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure4) N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid
5) Nitrilodiessigsäure-3-propionsäure5) Nitrilodiacetic acid-3-propionic acid
6) Isoserin-N,N-diessigsäure6) Isoserine-N, N-diacetic acid
7) Glucamin-N,N-diessigsäure7) Glucamine-N, N-diacetic acid
8) Hydroxyethyliminodiessigsäure •8) hydroxyethyliminodiacetic acid •
9) Nitrilotriessigsäure (NTA)9) Nitrilotriacetic acid (NTA)
Die Struktur der Inhibitoren ergibt sich aus der Zusammen¬ stellung in Tab.l.The structure of the inhibitors results from the compilation in Tab.l.
II) VergleichsSubstanzII) Comparative substance
A) Ethylendiamintetraessigsäure .(.EDTA) Tab.1; Eingesetzte Inhibitoren nach Formel (I)A) ethylenediaminetetraacetic acid. (. EDTA) Tab. 1; Inhibitors used according to formula (I)
III) Anwendungstechnische BeispieleIII) Examples of application technology
Beispiele 1 bis 9, Vergleichsbeispiele V 1 und V2Examples 1 to 9, comparative examples V1 and V2
Ein handelsübliches Ci2/14-κ°kosfettalkohol-2EO-ethersulfat- Na-Salz (Texapon(R) , 26,5 gew.-%ig in Wasser, Fa. Henkel KGaA, Düsseldorf, FRG) wurde mit einem Gehalt an 10 ppm Eisen (in Form von Eisen-(III)-Chlorid) sowie gegebenenfalls 150 ppm Inhibitor - jeweils bezogen auf den Feststoffgehalt der Produkte - versetzt. Die Muster wurden in durchsichtigen Flaschen bei Tageslicht und pH = 7 bis 7,5 über einen Zeit¬ raum von 3 Monaten gelagert. Nach Abschluß der Lagerversuche wurden die Farbzahlen der Testprodukte mit Hilfe eines Lovi- bond-Tintometers bestimmt. Die Ergebnisse sind in Tab.2 zu¬ sammengefaßt: A commercial Ci2 / 14- κ ° kosfettalkohol-2EO ether sulfate Na salt (Texapon ( R ), 26.5 wt .-% in water, Henkel KGaA, Dusseldorf, FRG) was with a content of 10 ppm Iron (in the form of iron (III) chloride) and optionally 150 ppm inhibitor - in each case based on the solids content of the products - added. The samples were stored in transparent bottles in daylight and pH = 7 to 7.5 over a period of 3 months. After the storage tests were completed, the color numbers of the test products were determined using a Lovibond tintometer. The results are summarized in Tab. 2:
Tab.2: Inhibierungsgrad der EisenverfärbungTab. 2: Degree of inhibition of iron discoloration
Beispiele 10 bis 16; Vergleichsbeispiele V3 bis V5Examples 10 to 16; Comparative examples V3 to V5
Das aus den Beispielen 1 bis 9 bekannte Ethersulfat wurde mit 40 ppm Eisen und 150 ppm Inhibitor - jeweils bezogen auf den Feststoffgehalt der Produkte - dotiert und über einen Zeit¬ raum von 21 d bei pH-Werten im Bereich von 8 bis 11 wie zuvor beschrieben gelagert. Die Farbzahlen sind Tab.3 zu entnehmen.The ether sulfate known from Examples 1 to 9 was doped with 40 ppm iron and 150 ppm inhibitor - in each case based on the solids content of the products - and over a period of 21 d at pH values in the range from 8 to 11 as previously described stored. The color numbers are shown in Tab. 3.
Tab.3: Inhibierungsgrad der Eisenverfärbung (II)Tab. 3: Degree of inhibition of iron discoloration (II)
III) Biologische AbbaubarkeitIII) Biodegradability
Die biologische Abbaubarkeit der untersuchten Inhibitoren wurde gemäß "OECD Screeningtest" (MOST) bzw. "Geschlossenen Flaschentest" (GF) bestimmt. Die Ergebnisse sind in Tab.4 zusammengefaßt:The biodegradability of the inhibitors examined was determined in accordance with the "OECD Screening Test" (MOST) or "Closed Bottle Test" (GF). The results are summarized in Tab. 4:
Tab. 4; Biologische AbbaubarkeitTab. 4; Biodegradability
Legende; - nicht bestimmtLegend; - not determined
DOC de and oxygen carbon BSB30/CSB Quotient aus "Biologischem Sauerstoff¬ bedarf" und "Chemischem Sauerstoffbe¬ darf" über den Meßzeitraum 30 d. DOC de and oxygen carbon BOD30 / COD quotient from "biological oxygen requirement" and "chemical oxygen requirement" over the measurement period 30 d.

Claims

Patentansprüche Claims
1. Verfahren zur Farbstabilisierung von Tensiden, bei dem man ihnen mindestens einen Farbinhibitor der Formel (I) zusetzt,1. Process for color stabilization of surfactants, in which at least one color inhibitor of the formula (I) is added to them,
R1 R3 R 1 R 3
I II I
HOOC-(CH )n-CH-N-CH-(CH2)m-R4 (I)HOOC- (CH) n -CH-N-CH- (CH 2 ) m -R 4 (I)
I R2 in derI R2 in the
R und R3 unabhängig voneinander für Wasserstoff oder eine Carboxylgruppe, R2 für Wasserstoff oder eine CH2C00H-Gruppe, R4 für eine Carboxyl-, Hydroxyl-, CH(OH)COOH- oderR and R 3 independently of one another for hydrogen or a carboxyl group, R2 for hydrogen or a CH2C00H group, R 4 for a carboxyl, hydroxyl, CH (OH) COOH or
(CH0H)5H-Gruppe sowie n und m unabhängig für 0 oder 1(CH0H) 5H group and n and m independently for 0 or 1
steht.stands.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man anionische Tenside stabilisiert, die ausgewählt sind aus der Gruppe, die von Alkylbenzolsulfonaten, Alkylsul- fonaten, Olefinsulfaten, Alkylethersulfonaten, Glycerin¬ ethersulfonaten, o_-Methylestersulfonaten, Sulfofettsäu- ren, Alkylsulfaten, Fettalkoholethersulfaten, Glycerin¬ ethersulfaten, Hydroxy ischethersulfaten, Monoglycerid- (ether)sulfaten, Fettsäureamid-(ether)Sulfaten, Sulfo- succinaten, Sulfosuccinamaten, Sulfotriglyceriden, Ethercarbonsäuren, Alkyloligoglucosidsulfaten und Al- kyl(ether)-phosphaten gebildet wird.2. The method according to claim 1, characterized in that anionic surfactants are stabilized, which are selected from the group consisting of alkylbenzenesulfonates, alkyl sulfonates, olefin sulfates, alkyl ether sulfonates, glycerol ether sulfonates, o-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates , Glycerol ether sulfates, hydroxy isomer sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, Ether carboxylic acids, alkyl oligoglucoside sulfates and alkyl (ether) phosphates is formed.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man nichtionische Tenside stabilisiert, die ausgewählt sind aus der Gruppe, die von Fettalkoholethoxylaten, Polyolfettsäureestern, Alkyloligoglycosiden, Sorbitan¬ estern und Polysorbaten gebildet wird.3. The method according to claim 1, characterized in that stabilizing nonionic surfactants which are selected from the group consisting of fatty alcohol ethoxylates, polyol fatty acid esters, alkyl oligoglycosides, sorbitan esters and polysorbates.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man amphotere bzw. zwitterionische Tenside stabilisiert, die ausgewählt sind aus der Gruppe, die von Alkylamido- betainen, Aminopropionaten, Aminoglycinaten, Imidazo- liniumbetainen und Sulfobetainen sind.4. The method according to claim 1, characterized in that stabilizing amphoteric or zwitterionic surfactants which are selected from the group consisting of alkylamidobetaines, aminopropionates, aminoglycinates, imidazoline betaines and sulfobetaines.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man wäßrige Tenside stabilisiert, die einen Feststoff- gehalt von 5 bis 85 Gew.-% - bezogen auf die Produkte - aufweisen.5. The method according to claim 1, characterized in that stabilizing aqueous surfactants which have a solids content of 5 to 85 wt .-% - based on the products.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Inhibitoren N-(l,2-Dicarboxy-2-hydroxyethyl)- glycerin, N-(1,2-Dicarboxy-2-hydroxyethyl)asparagin¬ säure, Isoserin-N,N-diessigsäure und/oder Nitrilotri- essigsäure einsetzt.6. The method according to claim 1, characterized in that the inhibitors are N- (1,2-dicarboxy-2-hydroxyethyl) glycerol, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid, isoserine-N , N-diacetic acid and / or nitrilotriacetic acid.
7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Inhibitoren in Mengen von 10 bis 1500 ppm - be¬ zogen auf den Feststoffgehalt der Produkte - einsetzt. 7. The method according to claim 1, characterized in that the inhibitors are used in amounts of 10 to 1500 ppm - based on the solids content of the products.
8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Tenside auf einen pH-Wert von 7 bis 11 ein¬ stellt. 8. The method according to claim 1, characterized in that the surfactants are adjusted to a pH of 7 to 11.
EP93912702A 1992-05-18 1993-05-11 Process for stabilizing the colour of surfactants Ceased EP0641379A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4216363A DE4216363A1 (en) 1992-05-18 1992-05-18 Process for color stabilization of surfactants
DE4216363 1992-05-18
PCT/EP1993/001149 WO1993023515A1 (en) 1992-05-18 1993-05-11 Process for stabilizing the colour of surfactants

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EP0641379A1 true EP0641379A1 (en) 1995-03-08

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JP (1) JPH07506762A (en)
DE (1) DE4216363A1 (en)
WO (1) WO1993023515A1 (en)

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ZA97698B (en) * 1996-01-30 1998-07-28 Colgate Palmolive Co Composition
US5843876A (en) * 1996-01-30 1998-12-01 Colgate-Palmolive Co. Composition
US5840670A (en) * 1996-01-30 1998-11-24 Colgate-Palmolive Co. Composition
CA2244782C (en) * 1996-01-30 2005-09-13 Colgate-Palmolive Company Cleansing composition comprising color stabilizer(s) and surfactant(s)
EP0892040B1 (en) * 1997-07-16 2003-03-05 Nippon Shokubai Co., Ltd. Use of Chelating compositions for cleaning
JP6462338B2 (en) * 2013-11-29 2019-01-30 川研ファインケミカル株式会社 Cosmetics containing amino sugar derivatives
DE102013225591A1 (en) * 2013-12-11 2015-06-11 Henkel Ag & Co. Kgaa Machine dishwashing detergent containing N-based complexing agents

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GB1565807A (en) * 1975-12-18 1980-04-23 Uilever Ltd Process and compositions for cleaning fabrics
US4560492A (en) * 1984-11-02 1985-12-24 The Procter & Gamble Company Laundry detergent composition with enhanced stain removal
US4769168A (en) * 1985-08-05 1988-09-06 Colgate-Palmolive Company Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use

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JPH07506762A (en) 1995-07-27
DE4216363A1 (en) 1993-11-25
WO1993023515A1 (en) 1993-11-25

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