EP0497337B1 - Aqueous suspensions of peroxycarboxylic acids - Google Patents

Aqueous suspensions of peroxycarboxylic acids Download PDF

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Publication number
EP0497337B1
EP0497337B1 EP92101532A EP92101532A EP0497337B1 EP 0497337 B1 EP0497337 B1 EP 0497337B1 EP 92101532 A EP92101532 A EP 92101532A EP 92101532 A EP92101532 A EP 92101532A EP 0497337 B1 EP0497337 B1 EP 0497337B1
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Prior art keywords
suspension
surfactant
acid
weight
ethoxylated
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German (de)
French (fr)
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EP0497337A2 (en
EP0497337A3 (en
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Gerd Dr. Reinhardt
Vera Fridrichs
Ulrike Rudolf
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Clariant Produkte Deutschland GmbH
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Hoechst AG
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    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D3/3947—Liquid compositions
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • EP 176.124 claims aqueous, flowable formulations consisting of peroxidicarboxylic acids and anionic surfactants, in particular alkylbenzenesulfonates.
  • peroxidicarboxylic acids in particular alkylbenzenesulfonates.
  • anionic surfactants in particular alkylbenzenesulfonates.
  • mixtures of linear alkylbenzenesulfonate and ethoxylated fatty alcohols are preferred as surfactants.
  • the aqueous suspension consists of a diperoxycarboxylic acid, alkylbenzenesulfonate, magnesium sulfate and water.
  • the essential components of the suspension according to the invention are therefore a peroxycarboxylic acid, a combination of two nonionic surfactants, and optionally further additional components. These are described in more detail below.

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

Description

Die vorliegende Erfindung betrifft die Herstellung lagerstabiler, wäßriger Suspensionen von festen Peroxicarbonsäuren und ihre Verwendung in Oxidations-, Bleich- und Desinfektionsmitteln.The present invention relates to the production of storage-stable, aqueous suspensions of solid peroxycarboxylic acids and their use in oxidizing agents, bleaching agents and disinfectants.

Neben anorganischen Persalzen wie Natriumperborat, Mono- oder Tetrahydrat und Aktivatorsystemen auf Basis von Tetraacetylethylendiamin (TAED) erlangen derzeit stabile organische Peroxicarbonsäuren zunehmend an Bedeutung als Bleichsysteme für die Wasch- und Reinigungsmittelindustrie.In addition to inorganic persalts such as sodium perborate, mono- or tetrahydrate and activator systems based on tetraacetylethylene diamine (TAED), stable organic peroxycarboxylic acids are currently becoming increasingly important as bleaching systems for the detergent and cleaning agent industry.

Einsatzgebiete für solche Bleichsysteme sind pulverförmige Waschpulver, Fleckensalze oder Spezialreiniger wie Gardinen- oder Geschirrspülmittel, aber auch Gebißreiniger. Sie sind weiterhin ein wesentlicher Bestandteil von Baukastensystemen.Areas of application for such bleaching systems are powdered washing powder, stain salts or special cleaners such as curtains or dishwashing detergents, but also denture cleaners. They continue to be an integral part of modular systems.

Wegen ungenügender Lagerstabilität können organische Peroxicarbonsäuren in pulverförmigen Wasch- und Reinigunsmitteln nur in Form stabilisierter Granulate eingesetzt werden. Bei leicht zersetzlichen Peroxicarbonsäuren ist zusätzlich die Einarbeitung von exothermic control agents notwendig, damit eine sichere Handhabbarkeit der Verbindungen gewährleistet wird. Da zur Granulierung in den meisten Fällen Peroxicarbonsäure-Pulver eingesetzt werden, entstehen darüberhinaus erhebliche Trocknungskosten.Due to insufficient storage stability, organic peroxycarboxylic acids in powder detergents and cleaning agents can only be used in the form of stabilized granules. In the case of easily decomposable peroxycarboxylic acids, the incorporation of exothermic control agents is also necessary to ensure that the connections can be handled safely. Since peroxycarboxylic acid powder is used for granulation in most cases will also incur significant drying costs.

Der Vorteil flüssiger Bleich- und Reinigungssysteme ist demgegenüber ihre einfache Herstellung, bei der keine kostenintensive Verfahrens- oder Trockenschritte notwendig sind. Die Herstellung ist in einfachen Anlagen auszuführen und zudem sind Peroxicarbonsäuren in feuchtem Zustand stand meist gefahrloser zu handhaben als in trockenemThe advantage of liquid bleaching and cleaning systems, in contrast, is their simple manufacture, in which no costly process or drying steps are necessary. The production is to be carried out in simple systems and, moreover, peroxycarboxylic acids are usually safer to handle when moist than when dry

Voraussetzung für einen kommerziellen Einsatz sind physikalisch stabile, fließfähige oder pastöse Suspensionen organischer Peroxicarbonsäuren, die ohne nennenswerten Verlust an Aktivsauerstoff längere Zeit problemlos lagerbar sind.A prerequisite for commercial use are physically stable, flowable or pasty suspensions of organic peroxycarboxylic acids, which can be stored for a long time without any significant loss of active oxygen.

Zur Herstellung und Verwendung solcher Bleichmittelsuspensionen sind eine Reihe von Patentanmeldungen erschienen.A number of patent applications have been published for the production and use of such bleaching agent suspensions.

So wird in US 3,996,152 ein Bleichmittel beschrieben, das eine Suspension einer festen Peroxicarbonsäure in einem flüssigen Carriermaterial und einen nicht stärkehaltigen Verdicker auf Polymerbasis enthält. Bevorzugte Persäure ist in diesem Falle die Peroxiazelainsäure. Verdicker auf Stärkebasis werden in US 4,017,412 beschrieben, jedoch neigen diese Formulierung nach längeren Lagerzeiten zu Phasenseparationen und werden somit unbrauchbar. Bleichmittelsuspensionen auf der Basis von kolloidaler Kieselsäure, Xanthan- oder Agar-Polysacchariden werden in EP-A 283,791 und 283,792 beansprucht. Die verwendete Peroxicarbonsäure wird dabei in phlegmatisierter Form eingesetzt.No. 3,996,152 describes a bleaching agent which contains a suspension of a solid peroxycarboxylic acid in a liquid carrier material and a polymer-based thickener which does not contain starch. In this case, preferred peracid is peroxiazelaic acid. Starch-based thickeners are described in US Pat. No. 4,017,412, but this formulation tends to phase separate after prolonged storage and is therefore unusable. Bleach suspensions based on colloidal Silicic acid, xanthan or agar polysaccharides are claimed in EP-A 283,791 and 283,792. The peroxycarboxylic acid used is used in a desensitized form.

Gießbare Persäureformulierungen ohne Zusatz eines Verdickers sind in EP 160,342 beschrieben. Dabei wird Dodecandiperoxisäure in einen wäßrigen Medium, das Tenside und Elektrolyte (Natriumsulfat oder -nitrat) enthält, bei pH-Werten zwischen 1 und 6.5 suspendiert. Als oberflächenaktive Verbindungen werden Mischungen anionischer und nichtionischer Tenside verwendet.Pourable peracid formulations without the addition of a thickener are described in EP 160,342. Dodecanediperoxy acid is suspended in an aqueous medium containing surfactants and electrolytes (sodium sulfate or nitrate) at pH values between 1 and 6.5. Mixtures of anionic and nonionic surfactants are used as surface-active compounds.

In EP 176,124 werden wäßrige, fließfähige Formulierungen, bestehend aus Peroxidicarbonsäuren und anionischen Tensiden, insbesondere Alkylbenzolsulfonaten, beansprucht. In EP 201,958 werden Gemische aus linearem Alkylbenzolsulfonat und ethoxilierten Fettalkoholen als Tenside bevorzugt. In einer ähnlichen Anmeldung (EP 240,481) besteht die wäßrige Suspension aus einer Diperoxicarbonsäure, Alkylbenzolsulfonat, Magnesiumsulfat und Wasser.EP 176.124 claims aqueous, flowable formulations consisting of peroxidicarboxylic acids and anionic surfactants, in particular alkylbenzenesulfonates. In EP 201,958, mixtures of linear alkylbenzenesulfonate and ethoxylated fatty alcohols are preferred as surfactants. In a similar application (EP 240,481), the aqueous suspension consists of a diperoxycarboxylic acid, alkylbenzenesulfonate, magnesium sulfate and water.

Wegen ökologischer Bedenken gegenüber linearem Alkylbenzolsulfonat (Geschwindigkeit und Vollständigkeit der biologischen Abbaubarkeit) werden in den Patentanmeldungen EP-A 334,405 und 337,516 unbedenklichere Alkansulfonate als anionische Tenside bevorzugt. Sie werden in Kombination mit ethoxylierten Alkoholen (EP-A 334,405) oder Fettsäuren (EP-A 337,516) verwendet.Because of ecological concerns about linear alkylbenzenesulfonate (speed and completeness of biodegradability), more harmless alkanesulfonates are preferred as anionic surfactants in patent applications EP-A 334,405 and 337,516. They are used in combination with ethoxylated alcohols (EP-A 334.405) or fatty acids (EP-A 337.516).

Suspensionen organischer Peroxicarbonsäuren in nichtionischen Tensiden mit HLB-Werten zwischen 6 und 11 werden in EP-A 386,566 beschrieben.Suspensions of organic peroxycarboxylic acids in nonionic surfactants with HLB values between 6 and 11 are described in EP-A 386,566.

Von wenigen Ausnahmen abgesehen, ist die verwendete Peroxicarbonsäure die Diperoxidodecandisäure (DPDDA). Diese ist jedoch in nicht phlegmatisierter Form nur unter größten Sicherheitsmaßnahmen handhabbar.With a few exceptions, the peroxycarboxylic acid used is diperoxidodecanedioic acid (DPDDA). However, this can only be handled in a non-desensitized form with the greatest security measures.

Mit den Imidoperoxicarbonsäuren (EP-A 325,288; EP-A 349,940; DE 38 23 172) und den Ureidoperoxicarbonsäuren (DE 40 16 980) wurden Gruppen organischer Peroxicarbonsäuren entwickelt, die eine deutlich höhere Oxidations- und Bleichkraft als die bisher verwendete Dodecandipersäure aufweisen. Wirtschaftlich und anwendungstechnisch von besonderem Interesse sind hierbei Phthalimidoperoxicapronsäure (PAP) und Phenylureidoperoxicapronsäure.With the imidoperoxycarboxylic acids (EP-A 325,288; EP-A 349,940; DE 38 23 172) and the ureidoperoxycarboxylic acids (DE 40 16 980) groups of organic peroxycarboxylic acids have been developed which have a significantly higher oxidation and bleaching power than the previously used dodecanediperic acid. Phthalimidoperoxicaproic acid (PAP) and phenylureidoperoxicaproic acid are of particular economic and technical interest.

Ziel der vorliegenden Erfindung war daher die Herstellung fließfähiger oder pastöser, lagerstabiler Persäuresuspensionen, insbesondere solchen auf Basis von Imido- und eidoperoxicarbonsäuren.The aim of the present invention was therefore the production of flowable or pasty, storage-stable peracid suspensions, in particular those based on imido and eidoperoxycarboxylic acids.

Die Aufgabe wurde dadurch gelöst, daß die Persäure in einem elektrolytfreien, wäßrigen Gemisch aus zwei verschiedenartigen nichtionischen Tensiden suspendiert wird. Überraschenderweise sind solche Suspensionen nicht nur physikalisch und chemisch über einen längeren Zeitraum stabil, von Vorteil ist insbesondere, daß durch eine geeignete Kombination der Tenside die Viskosität der Suspension in einem weiten Bereich variert werden kann. Durch Variation des Mischungsverhältnisses der beiden Tenside kann man sowohl zu niedrig viskosen Suspensionen, wie sie z.B. in Mehrkomponentenwaschmaschinen verwendet werden, als auch zu pastösen Suspensionen gelangen, die sich vor allen Dingen für eine gezielte Fleckbehandlung durch Auftragen der Paste auf das Gewebe eignen. Dies bietet einen deutlichen Vorteil gegenüber den in EP-A 386,566 beschriebenen Suspensionen, wo ausschließlich solche oxethylierten Fettalkohole genommen werden, deren HLB-Wert zwischen 6 und 11 liegt. Bei diesen Suspensionen ist eine derartige Variation in der Viskosität, wie sie bei den erfindungsgemäßen Suspensionen möglich ist, nicht gegeben.The object was achieved in that the peracid is suspended in an electrolyte-free, aqueous mixture of two different nonionic surfactants. Surprisingly, such suspensions are not only physically and chemically stable over a longer period of time, it is particularly advantageous that the viscosity of the suspension is achieved by a suitable combination of the surfactants can be varied in a wide range. By varying the mixing ratio of the two surfactants, both low-viscosity suspensions, such as those used in multi-component washing machines, and pasty suspensions can be obtained, which are particularly suitable for targeted stain treatment by applying the paste to the fabric. This offers a clear advantage over the suspensions described in EP-A 386,566, where only those ethoxylated fatty alcohols are used whose HLB value is between 6 and 11. With these suspensions, there is no such variation in viscosity as is possible with the suspensions according to the invention.

Gegenstand der Erfindung sind lagerstabile wäßrige Suspensionen von organischen Persäuren, die 1 bis 50 Gew.-% einer Tensidmischung, bestehend aus 1 bis 4 Gew.-Teilen eines C8-C22-Fettalkohols, oxethyliert mit 1 bis 5 Einheiten Ethylenoxid, und 4 bis 1 Gew.-Teilen eines C8-C22-Fettalkohols, oxethyliert mit 6 bis 25 Einheiten Ethylenoxid, sowie gegebenenfalls zusätzlich weitere übliche Komponenten enthalten.The invention relates to storage-stable aqueous suspensions of organic peracids which contain 1 to 50% by weight of a surfactant mixture consisting of 1 to 4 parts by weight of a C 8 -C 22 fatty alcohol, ethoxylated with 1 to 5 units of ethylene oxide, and 4 up to 1 part by weight of a C 8 -C 22 fatty alcohol, ethoxylated with 6 to 25 units of ethylene oxide, and, if appropriate, additionally contain further customary components.

Die wesentlichen Komponenten der erfindungsgemäßen Suspension sind daher eine Peroxicarbonsäure, eine Kombination zweier nichtionischer Tenside, sowie gegebenenfalls weitere zusätzliche Komponenten. Diese werden im Folgenden näher beschrieben.The essential components of the suspension according to the invention are therefore a peroxycarboxylic acid, a combination of two nonionic surfactants, and optionally further additional components. These are described in more detail below.

Die PeroxicarbonsäureThe peroxycarboxylic acid

Als Peroxicarbonsäuren können in den erfindungsgemäßen Formulierungen alle festen, bei pH 2-6 nahezu wasserunlöslichen Peroximono- oder -dicarbonsäuren eingesetzt werden. Eine Übersicht solcher Peroxicarbonsäuren ist z.B. in US 4,391,724 gegeben. Bevorzugt sind solche Persäuren, die durch eine spezielle, heteroatom-haltige Gruppe im Molekül zusätzlich stabilisiert sind. Solche Gruppen sind z.B. Amidogruppen wie in EP-A 170,386 und 290,292, Sulfongruppen wie in EP-A 267,175 oder 334,427, Aminogruppen, wie in EP-A 300,461, 316,809 und 340,754 beschrieben. Insbesondere bevorzugt sind aber Imidoperoxicarbonsäuren wie in EP-A 325 288, 325 289, 349,940 oder in DE 38 23 172 und Ureidoperoxicarbonsäuren wie in DE 40 16 980 beschrieben.Peroxicarboxylic acids which can be used in the formulations according to the invention are all solid peroximono- or dicarboxylic acids which are almost water-insoluble at pH 2-6. An overview of such peroxycarboxylic acids is e.g. given in US 4,391,724. Preferred peracids are those which are additionally stabilized in the molecule by a special heteroatom-containing group. Such groups are e.g. Amido groups as in EP-A 170,386 and 290,292, sulfone groups as in EP-A 267,175 or 334,427, amino groups as described in EP-A 300,461, 316,809 and 340,754. However, imidoperoxycarboxylic acids as described in EP-A 325 288, 325 289, 349.940 or in DE 38 23 172 and ureidoperoxycarboxylic acids as described in DE 40 16 980 are particularly preferred.

Die Konzentration der Peroxicarbonsäure in der erfindungsgemäßen Formulierung beträgt 0.5-30, vorzugsweise 3-20%. Die Teilchengröße der verwendeten Peroxicarbonsäure kann zwischen 0.5 und 1000 Mikrons betragen. Für eine schnelle Auflösung in der Waschflotte sind Teilchengrößen von 0.5 - 15 Mikrons empfehlenswert.The concentration of the peroxycarboxylic acid in the formulation according to the invention is 0.5-30, preferably 3-20%. The particle size of the peroxycarboxylic acid used can be between 0.5 and 1000 microns. Particle sizes of 0.5 - 15 microns are recommended for rapid dissolution in the wash liquor.

Das TensidsystemThe surfactant system

Das Tensidsystem für die erfindungsgemäßen Suspensionen besteht aus einer Kombination eines niederethoxylierten Fettalkohols und eines mittel- bis hochethoxylierten Fettalkohols. Dies bedeutet, daß das erste Tensid 1-5, vorzugsweise 2-4 Mol Ethylenoxid, das zweite Tensid 6 bis 25 Mol, vorzugsweise 6-12 Mol Ethylenoxid pro Mol Alkohol enthält. Der Fettalkohol selbst enthält 8 - 22, vorzugsweise 12 - 18 C-Atome.The surfactant system for the suspensions according to the invention consists of a combination of a low ethoxylated Fatty alcohol and a medium to highly ethoxylated fatty alcohol. This means that the first surfactant contains 1-5, preferably 2-4 moles of ethylene oxide, the second surfactant 6 to 25 moles, preferably 6-12 moles of ethylene oxide per mole of alcohol. The fatty alcohol itself contains 8-22, preferably 12-18, carbon atoms.

Die in diesen Tensiden vorliegenden Alkohole können natürlichen oder petrochemischen Ursprungs, verzweigt oder geradkettig sein. Beispiele für niederethoxylierte Alkohole sind die Handelsprodukte Genapol UD-030, 050, Genapol C-050, Genapol O-020, 050, Genapol OA-040, Genapol OX-030, Genapol T-050 oder Genapol X-030, 050. Bespiele für mittel- oder hochethoxylierte Alkohole sind Genapol OA-070, 080, 089, Genapol OX-060, 080, 100, 109, 130, Genapol O-080, 100, 120, 150, Genapol C-080, 100, Genapol UD-079, 080, 088, 110, Genapol T-080, 100, 110, 150, 180 oder Genapol X-060, 080, 150. (Genapol ist ein eingetragenes Warenzeichen der HOECHST AG). Die Fettalkoholreste der Tenside können gleich oder verschieden sein.The alcohols present in these surfactants can be of natural or petrochemical origin, branched or straight-chain. Examples of low-ethoxylated alcohols are the commercial products Genapol UD-030, 050, Genapol C-050, Genapol O-020, 050, Genapol OA-040, Genapol OX-030, Genapol T-050 or Genapol X-030, 050. Examples of Medium or highly ethoxylated alcohols are Genapol OA-070, 080, 089, Genapol OX-060, 080, 100, 109, 130, Genapol O-080, 100, 120, 150, Genapol C-080, 100, Genapol UD-079 , 080, 088, 110, Genapol T-080, 100, 110, 150, 180 or Genapol X-060, 080, 150. (Genapol is a registered trademark of HOECHST AG). The fatty alcohol residues of the surfactants can be the same or different.

Das Mischungsverhältnis beider Tenside ist von entscheidender Bedeutung für das Viskositätsverhalten der erfindungsgemäßen Suspensionen. Es kann in weiten Bereichen variiert werden. Bevorzugt werden Mischungsverhältnisse der nieder- zu mittel-bzw. hochethoxylierten Fettalkohole von 1:4 bis 4:1. Insbesondere bevorzugt werden Tensidmischungen, in denen die Tenside im Verhältnis von 1:2 bis 2:1 vorliegen. Das Viskositätsverhalten der erfindungsgemäßen Suspensionen ist aber auch abhängig von ihrem Gesamttensidgehalt. Der Gehalt der Tenside in der wäßrigen Suspension liegt zwischen 1 und 50%, vorzugsweise zwischen 2 und 30%, insbesondere aber zwischen 3 und 25%.The mixing ratio of the two surfactants is of crucial importance for the viscosity behavior of the suspensions according to the invention. It can be varied in a wide range. Mixing ratios of the low to medium or. highly ethoxylated fatty alcohols from 1: 4 to 4: 1. Surfactant mixtures in which the surfactants are present in a ratio of 1: 2 to 2: 1 are particularly preferred. The viscosity behavior of the suspensions according to the invention is also dependent on their Total surfactant content. The content of the surfactants in the aqueous suspension is between 1 and 50%, preferably between 2 and 30%, but in particular between 3 and 25%.

Zusätzliche KomponentenAdditional components

Da Schwermetallionen die Zersetzung von Peroxiverbindungen katalysieren, kann die erfindungsgemäße Suspension Komplexiermittel enthalten, um diese Ionen zu komplexieren. Beispiele für solche Komplexiermittel sind Ethylendiamintetraessigsäure (EDTA), Nitrilotriessigsäure (NTA), Isoserindiessigsäure, Ethylendiamintetramethylenphosphonsäure (EDTMP), insbesondere aber Diethylentriaminpentamethylen-phosphonsäure. Die Konzentration dieser Verbindungen kann zwischen 10 ppm und 8%, vorzugsweise 0.1 - 5% betragen. In speziellen Anwendungen z.B. bei der Entfernung bluthaltiger Anschmutzungen kann eine hohe Konzentration (d.h. 3-5%) dieser Stoffe erwünscht sein. Die Verbindungen können in Form der freien Säure, teilneutalisiert oder in Form der Salze zugegeben werden.Since heavy metal ions catalyze the decomposition of peroxy compounds, the suspension according to the invention can contain complexing agents in order to complex these ions. Examples of such complexing agents are ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), isoserinediacetic acid, ethylenediaminetetramethylenephosphonic acid (EDTMP), but especially diethylenetriaminepentamethylenephosphonic acid. The concentration of these compounds can be between 10 ppm and 8%, preferably 0.1-5%. In special applications e.g. a high concentration (i.e. 3-5%) of these substances may be desirable when removing blood-containing stains. The compounds can be added in the form of the free acid, partially neutralized or in the form of the salts.

Eine Zugabe von Mitteln zur Einstellung des pH-Wertes kann ebenfalls erforderlich sein, da die Formulierungen eine optimale chemische Stabilität im sauren pH-Bereich, insbesondere zwischen pH 2-6, vorzugsweise bei pH 3-5.5 aufweisen. Zur Ansäuerung der Suspension sind alle organischen oder anorganischen Säuren wie Salzsäure, Phosphorsäure, Schwefelsäure, Essigsäure, Zitronensäure, Milchsäure, zur Alkalisierung anorganische Basen oder organische Amine verwendbar.It may also be necessary to add agents for adjusting the pH, since the formulations have optimal chemical stability in the acidic pH range, in particular between pH 2-6, preferably at pH 3-5.5. All organic or inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, citric acid, Lactic acid, can be used for alkalizing inorganic bases or organic amines.

Als weitere Zusatzstoffe kann die erfindungsgemäße Formulierung Entschäumer, optische Aufheller, Parfümstoffe, Farbstoffe, Antioxidantien oder Wasserstoffperoxid enthalten.The formulation according to the invention can contain defoamers, optical brighteners, perfumes, dyes, antioxidants or hydrogen peroxide as further additives.

Die erfindungsgemäßen Peroxicarbonsäure-Supensionen lassen sich in zahlreichen Anwendungsgebieten einsetzen, so z.B. als Waschmitteladditiv für die Textilwäsche, als Waschkraftverstärker, in Light Duty Liquids, in Reinigungs- und Desinfektionsmitteln für harte Oberflächen, in Allzweckreinigern oder sauren Abresivreinigern.The peroxycarboxylic acid residues according to the invention can be used in numerous fields of application, for example as a detergent additive for textile washing, as a detergent booster, in light duty liquids, in cleaning agents and disinfectants for hard surfaces, in all-purpose cleaners or acidic abresive cleaners.

In Kombination mit einem flüssigen oder pulverförmigen Waschmittel werden Rotwein, Tee und andere bleichbare Anschmutzungen während des Wasch- bzw. Reinigungsprozesses bei 20-95°C problemlos entfernt. Insbesondere sind die gießbaren bzw. pumpfähigen Suspensionen als Bleichkomponente zum Einsatz in modernen Mehrkomponentenwaschmaschinen geeignet.In combination with a liquid or powder detergent, red wine, tea and other bleachable stains are easily removed during the washing or cleaning process at 20-95 ° C. In particular, the pourable or pumpable suspensions are suitable as bleaching components for use in modern multi-component washing machines.

Die erfindungsgemäßen Suspensionen können weiterhin als Einweichmittel oder Fleckenentferner eingesetzt werden. Dazu eignen sich insbesondere die hochviskosen Formulierungen, die direkt auf Anschmutzungen aufgetragen werden können. Pastöse Formulierungen können z.B. in Tuben oder in Form von Sticks in den Handel gebracht werden.The suspensions according to the invention can also be used as soaking agents or stain removers. The highly viscous formulations, which can be applied directly to soiling, are particularly suitable for this. Pasty formulations can be marketed, for example, in tubes or in the form of sticks.

Die Suspensionen werden in solchen Konzentrationen eingesetzt, daß der Aktivsauerstoffgehalt der Waschflotte zu Beginn des Waschprozesses 0.5-50ppm, vorzugsweise 3-30ppm Aktivsauerstoff beträgt.The suspensions are used in such concentrations that the active oxygen content of the wash liquor at the start of the washing process is 0.5-50 ppm, preferably 3-30 ppm active oxygen.

Beispiele 1-7:Examples 1-7:

Herstellung von flüssigen Bleichmitteln auf Basis von Phthaloylaminoperoxicapronsäure (PAP).Production of liquid bleaching agents based on phthaloylaminoperoxicaproic acid (PAP).

Die nichtionischen Tenside werden aufgeschmolzen und intensiv miteinander gemischt, warmes Wasser und ggf. Zusatzstoffe werden hinzufügt. Unter Rühren läßt man abkühlen, anschließend wird der pH-Wert mit H2SO4 auf < 4 eingestellt, dann erst wird die Peroxicarbonsäure langsam eingerührt und die Mischung homogenisiert.
Alle Angaben in Gew.%. Beispiel 1 2 3 4 5 6 7 C14/C15-Oxoalkohol mit 8 Einheiten Ethylenoxid 5 5 5 5 6 10 10 C11-Oxoalkohol mit 3 Einheiten Ethylenoxid 5 5 4 5 5 5 10 Dequest 2066 1) - - 1 1 1 0,5 2 Comperlan KD (R) 2) - - - - - 2 - Entschäumer - - - - - 2 - PAP 5 10 15 15 15 15 15 dest.Wasser ad 100% Viskosität in mPas: 200 850 1100 1200 1500 8000 hochpastös 1) Komplexiermittel 2) Fettsäurealkanolamid (Henkel KGaA) The nonionic surfactants are melted and mixed intensively, warm water and any additives are added. The mixture is allowed to cool with stirring, then the pH is adjusted to <4 using H 2 SO 4 , only then is the peroxycarboxylic acid slowly stirred in and the mixture is homogenized.
All figures in% by weight. example 1 2nd 3rd 4th 5 6 7 C 14 / C 15 oxo alcohol with 8 units of ethylene oxide 5 5 5 5 6 10th 10th C 11 oxo alcohol with 3 units of ethylene oxide 5 5 4th 5 5 5 10th Dequest 2066 1) - - 1 1 1 0.5 2nd Comperlan KD (R) 2) - - - - - 2nd - Defoamer - - - - - 2nd - PAP 5 10th 15 15 15 15 15 distilled water ad 100% Viscosity in mPas: 200 850 1100 1200 1500 8000 highly pasty 1) complexing agent 2) fatty acid alkanolamide (Henkel KGaA)

Alle Formulierung können mehr als 3 Monate gelagert werden, ohne daß eine Phasentrennung beobachtet wird. Die Formulierungen sind auch im Temperaturschaukeltest (-8°C bis +40°C) stabil. Der Aktivsauerstoffverlust betrug nach 3 monatiger Lagerung max. 15%, bestimmt durch jodometrische Titration vor und nach der Lagerung.All formulations can be stored for more than 3 months without phase separation being observed. The formulations are also stable in the temperature swing test (-8 ° C to + 40 ° C). The active oxygen loss after 3 months of storage was max. 15%, determined by iodometric titration before and after storage.

Beispiel 8:Example 8:

Waschversuche mit einer Formulierung gemäß Beispiel 4.Washing tests with a formulation according to Example 4.

Die Bleichwirksamkeit der erfindungsgemäßen Bleichmittelsuspensionen wurde in Waschversuchen überprüft.The bleaching effectiveness of the bleaching agent suspensions according to the invention was checked in washing tests.

Die Waschversuche wurden in einer Waschmaschine (Miele W 723) bei 40°C unter Verwendung von Wasser der Wasserhärte 15°dH durchgeführt. Die Hauptwaschzeit betrug 30 Minuten. Es wurden 4g/L der Formulierung gemäß Beispiel 4 eingesetzt. Auf den Zusatz eines separaten Waschmittels wurde verzichtet.The washing tests were carried out in a washing machine (Miele W 723) at 40 ° C using water with a water hardness of 15 ° dH. The main wash time was 30 minutes. 4 g / L of the formulation according to Example 4 were used. A separate detergent was not added.

Als Anschmutzungen dienten Rotwein auf Baumwolle (EMPA, Schweiz), Tee auf Baumwolle (WFK, Krefeld), Tee auf Polyester/Baumwolle (WFK, Krefeld) und Kaffee auf Baumwolle (WFK, Krefeld). Je zwei dieser Testanschmutzungen wurden auf ein Baumwolle-Frotteehandtuch aufgenäht. Jeweils zwei dieser Handtücher wurden zusammen mit 2 kg Balastwäsche pro Waschgang eingesetzt.Soiling served as red wine on cotton (EMPA, Switzerland), tea on cotton (WFK, Krefeld), tea on polyester / cotton (WFK, Krefeld) and coffee on cotton (WFK, Krefeld). Two of these test stains were sewn onto a cotton terry towel. Two of these towels were used together with 2 kg of ballast laundry per wash.

Die Aufhellung der Testanschmutzungen wurden nach der Wäsche durch Remissionsmessungen bestimmt. Die Waschversuche wurden nach 3 monatiger Lagerung der Formulierung 4 wiederholt. Zum Vergleich wurde mit einer Formulierung gemäß Beispiel 4 gewaschen, die jedoch keine Peroxicarbonsäure enthielt. Waschversuche mit Formulierung 4 Remissionswerte gemessen bei 460 nm neu nach 3 Monaten ohne Peroxicarbonsäure Anschmutzung: BW-Rotwein 75,4 73,8 53,5 BW-Kaffee 80,8 78,6 63,5 BW-Tee 77,2 73,6 43,9 PE-BW-Tee 86,7 84,2 48,8 The lightening of the test stains was determined after the wash by remission measurements. The washing tests were repeated after formulation 4 had been stored for 3 months. For comparison, washing was carried out with a formulation according to Example 4 which, however, did not contain any peroxycarboxylic acid. Washing experiments with formulation 4 reflectance values measured at 460 nm New after 3 months without peroxy carboxylic acid Soiling: BW red wine 75.4 73.8 53.5 BW coffee 80.8 78.6 63.5 BW tea 77.2 73.6 43.9 PE-BW tea 86.7 84.2 48.8

Die Waschergebnisse belegen die Bleichwirksamkeit der erfindungsgemäßen Formulierung. Nach einer Lagerzeit von 3 Monaten wird nur ein unwesentlicher Abfall der Bleichaktivität beobachtet.The washing results demonstrate the bleaching effectiveness of the formulation according to the invention. After a storage period of 3 months, only an insignificant drop in bleaching activity is observed.

Claims (12)

  1. A storage-stable aqueous suspension of an organic peracid, wherein the suspension contains 1 to 50% by weight of a surfactant mixture composed of 1 to 4 parts by weight of a C8-C22-fatty alcohol, ethoxylated with 1 to 5 units of ethylene oxide, and 4 to 1 parts by weight of a C8-C22-fatty alcohol, ethoxylated with 6 to 25 units of ethylene oxide.
  2. A suspension as claimed in claim 1, which is adjusted to a pH of 2 to 6.
  3. A suspension as claimed in claim 1, which contains a peracid which contains a heteroatom in the molecule.
  4. A suspension as claimed in claim 1, which contains an imido- or ureidoperoxycarboxylic acid as the peracid.
  5. A suspension as claimed in claim 1, wherein the content of peracid is 3 to 20% by weight.
  6. A suspension as claimed in claim 1, wherein the surfactant in the surfactant mixture is derived from C12-C18-fatty alcohols.
  7. A suspension as claimed in claim 1, wherein one surfactant in the surfactant mixture is ethoxylated with 2 to 4 units of ethylene oxide.
  8. A suspension as claimed in claim 1, wherein one surfactant in the surfactant mixture is ethoxylated with 6 to 12 units of ethylene oxide.
  9. A suspension as claimed in claim 1, wherein the surfactant mixture consists of 1 to 2 parts by weight of one surfactant and 2 to 1 parts by weight of the other surfactant.
  10. A suspension as claimed in claim 1, wherein the suspension contains 3 to 25% by weight of the surfactant mixture.
  11. A suspension as claimed in claim 1, wherein the suspension contains complexing agents, acid, antifoam agents, optical brighteners, perfumes, dyes, antioxidants and/or hydrogen peroxide as additional components.
  12. The use of the suspension as claimed in one or more of claims 1 to 11 in detergents, cleaners and bleaches.
EP92101532A 1991-02-01 1992-01-30 Aqueous suspensions of peroxycarboxylic acids Expired - Lifetime EP0497337B1 (en)

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AU642337B2 (en) 1993-10-14
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US5391324A (en) 1995-02-21
NO920418L (en) 1992-08-03
EP0497337A3 (en) 1992-11-19
AU1060992A (en) 1992-08-06
JPH0625697A (en) 1994-02-01
DE59208558D1 (en) 1997-07-10
TW291496B (en) 1996-11-21
NO920418D0 (en) 1992-01-31
HK1007166A1 (en) 1999-04-01
JP3193756B2 (en) 2001-07-30
KR920016587A (en) 1992-09-25
ZA92702B (en) 1992-10-28
BR9200330A (en) 1992-10-13
CA2060437A1 (en) 1992-08-02

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