EP0630415B1 - Degreasing agents - Google Patents
Degreasing agents Download PDFInfo
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- EP0630415B1 EP0630415B1 EP93906493A EP93906493A EP0630415B1 EP 0630415 B1 EP0630415 B1 EP 0630415B1 EP 93906493 A EP93906493 A EP 93906493A EP 93906493 A EP93906493 A EP 93906493A EP 0630415 B1 EP0630415 B1 EP 0630415B1
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- Prior art keywords
- fatty alcohol
- average
- components
- alcohols
- weight
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- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
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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
- C11D1/66—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
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C5/00—Degreasing leather
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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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the invention relates to the use of mixtures of special fatty alcohol ethoxylates for the degreasing of hides, skin, hide, leather.
- nonionic surfactants or surfactant mixtures and their solutions in selected auxiliary liquids, in particular organic solvents is of considerable importance in the production of leathers and furs in a plurality of work stages of the product classes concerned here.
- Compounds of this type are required in particular in the context of de-greasing - for example in the treatment of sheepskins or sheep's bare skin - as well as in general for surface degreasing or basic cleaning in switches, limbers and stains, but also in the course of further work steps in leather or fur production.
- nonionic emulsifiers of the type concerned here are addition compounds of ethylene oxide and / or propylene oxide with alkylphenols, fatty alcohols or fatty acids.
- the importance of the class of substances concerned here is, inter alia, that nonionic emulsifiers of the type described have virtually no binding capacity to the skin or leather fibers. They can thus optimally correspond to their function of solubilizing the skin fat without being hindered by interaction with the skin substance.
- Degreasing agents are known from German patent application DE-OS 25 22 902, which contain non-ionic and / or anionic surfactants as auxiliary agents.
- a mixture is specifically disclosed which contains 10% by weight of an anionic surfactant (alkylbenzenesulfonate), 10% by weight of an alcoholic solvent (isopropyl alcohol), 20% by weight of an adduct of 10 moles of ethylene oxide with C 12/18 -Fatty alcohol and 20 wt .-% of an adduct of 3 moles of ethylene oxide with C 10/12 fatty alcohol.
- a degreasing process based on such a mixture cannot satisfy on the one hand because of the abundance of the auxiliary substances required.
- the use of anionic surfactants and the use of solvents must be largely avoided in the course of ever-increasing environmental awareness.
- FR-A-2 303 850 describes surface-active mixtures based on mixtures of ethoxylated fatty alcohols. Use in detergents is mentioned as the intended use.
- GB-A-2 011 944 describes liquid detergents containing a ternary mixture of nonionic surfactants, these surfactants being high, medium and low ethoxylated fatty alcohols.
- the profile of requirements placed on work equipment of the type concerned according to the invention is, however, not limited to the required excellent emulsifying and dispersing capacity for fats, fatty acids, metal soaps and / or waxes as well as dirt residues of all kinds; rather, a large number of further requirements have to be met.
- the aid must be easy to wash out of the skin substance, and there should be no undesired interactions with other anionic, cationic and / or nonionic agents, for example dyes and fatliquoring agents.
- the desired degreasing agents should have sufficient resistance to electrolytes and, in particular, resistance to water hardness even at high levels of water hardness. Finally, the applicability should be guaranteed both in the acidic and in the alkaline pH range.
- the teaching of the invention is based on the object, in the context of the degreasing agents mentioned here based on nonionic fatty alcohol alkoxylates To develop an optimized degreasing agent that guarantees broad applicability to a wide variety of operating conditions with simultaneously optimized process results.
- the solution to this problem according to the invention lies in the targeted selection and mixing of different active ingredient components, which, however, can overall be assigned to a substance class that is biologically optimally compatible.
- the essence of the teaching according to the invention thus lies in the joint use of selected medium- to long-chain fatty alcohol ethoxylates - substance class (a) - and nonionic E0 compounds - substance class (b) - which are derived from the so-called preliminary fatty alcohols.
- the so-called preliminary fatty alcohols are preferably straight-chain representatives of the range below C 12 , in particular the range of approximately C 6-10 . Special meaning comes here in the sense of the teaching according to the invention the C 8 pre-fatty alcohol and / or its mixtures with C 10 pre-fatty alcohols.
- the alcohols on which components (a) and (b) are based those which are of natural origin are of particular importance.
- the corresponding alcohols of plant and / or animal origin are known to be obtained from the associated fatty acids of plant and / or animal origin by hydrogenation. These are at least largely predominantly alcohols or alcohol mixtures with an even C number.
- ethoxylates of the corresponding straight-chain and saturated C 12 -, C 14 , C 16 and C 18 alcohols are preferred as the base for the ethoxylates according to (a).
- the most important alcohol residue for the component to (b) is the C 8 pre-fatty alcohol.
- Component (a) selected as effective fat emulsifiers makes up the larger amount of the degreasing agent according to the invention based on the mixture of (a) and (b).
- the minor amount of component (b) is in the range from 2 to 25% by weight, based on the sum of (a) and (b). The range from 5 to 22% by weight is particularly preferred.
- this active ingredient component (b) fulfills an important function, in particular as a dispersing aid for facilitating the absorption and emulsification of fats, waxes and the like by the main active ingredient components of substance class (a) within the meaning of the teaching according to the invention.
- the combined use of predominant amounts of the emulsifiers (a) and minor amounts of the dispersants (b) is decisive for the improved work result sought and achieved according to the invention.
- these objectives are further promoted by a specific selection of components (a).
- the invention provides that mixtures of fatty alcohol ethoxylates of different average E0 grades are used as component (a). The range of up to 15 E0 units per molecule of the fatty alcohol is preferably not exceeded.
- Components (a1) and (a2) are preferably used in mixing ratios of at least 2: 1.
- the average degree of ethoxylation of components (b) - in adaptation to the shorter chain length of the alcoholic basic component present here - is significantly lower than in the emulsifier components (al) and / or (a2).
- Preferably C 8 precursor fatty alcohol ethoxylates having an average degree of ethoxylation of 1.5 to 2.5 are used as dispersant component (b).
- Particularly suitable active substance mixtures in the sense of the teaching according to the invention contain, for example, 55 to 70% by weight of the emulsifier component (a1) together with 20 to 30% by weight of the emulsifier component (a2) in addition to minor amounts of the dispersant component (b).
- the lower limit for the active ingredient components (b) is about 2% by weight, based on the sum of components (a) and (b), but preferably at least 5% by weight of component (b) in the active ingredient mixture are.
- the mixtures to be used according to the invention can contain further specially selected solvents.
- solvents are suitable which are capable of adequately dissolving, emulsifying and / or dispersing the auxiliaries or of the fats and waxes to be absorbed from the skin substance by their cooperation, special selection criteria are expedient and preferred here according to the invention:
- Solvents within the meaning of the requirements according to the invention are, in particular, corresponding organic liquids which are immiscible or only water-miscible to a limited extent and which are distinguished by sufficiently high flash points - usually flash points above 100 ° C.
- Appropriate organic components, which in turn are biodegradable, are preferred as solvents that flow at room temperature.
- carboxylic acid esters in particular esters of monofunctional carboxylic acids with monohydric alcohols, high-boiling ethers, corresponding oleophilic alcohols and / or carbonic acid esters which are flowable at room temperature can be used quite generally. It may be expedient to select representatives of unsaturated components on the side of the ester-forming carboxylic acids and / or the ester-forming alcohols, in particular in the class of the carboxylic acid esters.
- the unsaturated ester-forming components mentioned here are in turn preferably compounds which are still flowable at room temperature, so that small amounts of the auxiliary solvents remain in the skin or leather structure on an ester basis, even after a saponification or partial saponification which may occur later, do not lead to any undesired deposition of paraffin-like character.
- the amount of biodegradable solvent can vary within wide limits and can, for example, make up 5 to 95% by weight of the mixture of substances.
- the active ingredient mixture from the components of (a) and (b) preferably makes up about 5 to 90% by weight in such solvent-containing preparation forms.
- Appropriate solutions which contain 10 to 60% by weight of components (a) and (b) in a biodegradable solvent or solvent mixture are particularly suitable. The weight percentages given here refer to the total product.
- Suitable auxiliary solvents based on unsaturated esters are, in particular, compounds of corresponding olefinically unsaturated higher fatty acids, for example oleic acid, with optionally also unsaturated higher fatty alcohols, in particular oleyl alcohol.
- examples of the alcohol-based solvent phase are Guerbet alcohols, especially in the range up to C 20 .
- the selection of ethers and in particular oleophilic alcohols which are flowable under normal conditions can lead to improved work results with regard to the hydrolysis resistance of the biodegradable solvent used as the auxiliary liquid phase.
- sheep pimples are divided along the back line according to the following information.
- the right and left halves are identified as belonging to one another and then one half is processed in separate processes using the degreasing agents according to the invention and the other half using previously known standard or comparative products from the field of degreasing agents.
- the individual procedure is as follows:
- Table 1 The individual work results from each of several experiments are summarized in Table 1 below; the natural fat content of the pelts used (ie before the degreasing started) was 23-27% by weight.
- Table 1 No. De-greasing agent used Residual fat content after degreasing (in% by weight) a) 15% by weight organic solvent (petroleum) 4.0 - 6.0 1.5 wt% NP-10 b) 6 wt% NP-10 4.0 - 5.0 c) 6% by weight mixture of NP-10 with organic solvent (isopropyl alcohol) 3.0 - 4.0 d) 6% by weight product mixture of 90% Dehydol-LS7 and 10% C8-1E0 2.7 - 3.9 e) 6% by weight product mixture of 70% dehydol LS7 and 30% C8-1E0 4.8 - 5.9 Abbreviations in Table 1: NP-10 : adduct of 10 moles of ethylene oxide with 1 mole of nonyl
Abstract
Description
Die Erfindung betrifft die Verwendung von Gemischen spezieller Fettalkoholethoxylate zur Entfettung von Häuten, Blößen, Fellen, Ledern.The invention relates to the use of mixtures of special fatty alcohol ethoxylates for the degreasing of hides, skin, hide, leather.
Die Verwendung nichtionischer Tenside beziehungsweise Tensidgemische und ihrer Lösungen in ausgewählten Hilfsflüssigkeiten, insbesondere organischen Lösungsmitteln, hat bei der Herstellung von Ledern und Pelzen in einer Mehrzahl von Arbeitsstufen der hier betroffenen Produktklassen beträchtliche Bedeutung. Verbindungen dieser Art werden insbesondere im Rahmen der Blößenentfettung - zum Beispiel bei der Behandlung von Schaffellen beziehungsweise Schafblößen - sowie ganz allgemein für die Oberflächenentfettung beziehungsweise Grundreinigung in Weiche, Äscher und Beize aber auch im Rahmen weiterer Arbeitsstufen der Leder- beziehungsweise Pelzherstellung benötigt.The use of nonionic surfactants or surfactant mixtures and their solutions in selected auxiliary liquids, in particular organic solvents, is of considerable importance in the production of leathers and furs in a plurality of work stages of the product classes concerned here. Compounds of this type are required in particular in the context of de-greasing - for example in the treatment of sheepskins or sheep's bare skin - as well as in general for surface degreasing or basic cleaning in switches, limbers and stains, but also in the course of further work steps in leather or fur production.
Bekannte nichtionische Emulgatoren der hier betroffenen Art sind Additionsverbindungen von Ethylenoxid und/oder Propylenoxid an Alkylphenole, Fettalkohole oder Fettsäuren. Die Bedeutung der hier betroffenen Stoffklasse liegt unter anderem darin, daß nichtionische Emulgatoren der geschilderten Art praktisch kein Bindungsvermögen an die Haut- oder Lederfaser aufweisen. Sie können damit ihrer Funktion der Solubilisierung des Hautfettes optimal entsprechen, ohne durch Interaktion mit der Hautsubstanz behindert zu werden.Known nonionic emulsifiers of the type concerned here are addition compounds of ethylene oxide and / or propylene oxide with alkylphenols, fatty alcohols or fatty acids. The importance of the class of substances concerned here is, inter alia, that nonionic emulsifiers of the type described have virtually no binding capacity to the skin or leather fibers. They can thus optimally correspond to their function of solubilizing the skin fat without being hindered by interaction with the skin substance.
Eine der bislang am häufigsten eingesetzten Verbindungen dieser Tensidklasse zählt zur Gruppe der Alkylphenolethoxylate. Es handelt sich dabei um das im Mittel 10 EO-Gruppen aufweisende Nonylphenolethoxylat, das unter den verschiedensten Handelsnamen für das hier angesprochene Einsatzgebiet vertrieben wird. Das angestrebte technische Arbeitsergebnis bezüglich der Entfettung von Häuten und/oder Fellen wird optimal erfüllt. Gleichwohl bestehen Bedenken gegen den weiteren Einsatz dieses Arbeitsmittels. Seine Abbauprodukte können in biologischen Stufen von Kläranlagen zu Problemen führen.One of the most frequently used compounds of this class of surfactants so far belongs to the group of alkylphenol ethoxylates. It is the nonylphenol ethoxylate, which has an average of 10 EO groups and is marketed under a wide variety of trade names for the field of application mentioned here. The desired technical work result regarding the degreasing of hides and / or skins is optimally fulfilled. Nevertheless, there are concerns about the further use of this tool. Its degradation products can cause problems in biological stages of sewage treatment plants.
Die Fachwelt hat seit geraumer Zeit vergleichbare Produkte auf der Basis von Fettalkoholalkoxylaten entwickelt, die das gestellte Leistungsprofil wenigstens weitgehend erfüllen können, in der Abwasseraufbereitung jedoch weniger problematisch sind als die zuvor erwähnten alkylaromatischen Verbindungen.For some time now, experts have developed comparable products based on fatty alcohol alkoxylates, which can at least largely meet the performance profile, but are less problematic in wastewater treatment than the previously mentioned alkyl aromatic compounds.
So sind aus der deutschen Patentanmeldung DE-OS 25 22 902 Entfettungsmittel bekannt, die als Hilfsmittel nichtionische und/oder anionische Tenside enthalten. In Beispiel 1 ist konkret ein Gemisch offenbart, das 10 Gew.-% eines anionischen Tensids (Alkylbenzolsulfonat), 10 Gew.-% eines alkoholischen Lösungsmittels (Isopropylalkohol), 20 Gew.-% eines Anlagerungsproduktes von 10 Mol Ethylenoxid an C12/18-Fettalkohol und 20 Gew.-% eines Anlagerungsproduktes von 3 Mol Ethylenoxid an C10/12-FettaFkohol enthält. Ein Entfettungsverfahren auf Basis einer solchen Mischung kann jedoch einerseits wegen der Fülle der benötigten Hilfsstoffe, nicht befriedigen. Darüber hinaus ist im Zuge eines ständig wachsenden Umweltbewußtseins die Verwendung anionischer Tenside sowie die Verwendung von Lösungsmittel weitgehend zu vermeiden.Degreasing agents are known from German patent application DE-OS 25 22 902, which contain non-ionic and / or anionic surfactants as auxiliary agents. In example 1 a mixture is specifically disclosed which contains 10% by weight of an anionic surfactant (alkylbenzenesulfonate), 10% by weight of an alcoholic solvent (isopropyl alcohol), 20% by weight of an adduct of 10 moles of ethylene oxide with C 12/18 -Fatty alcohol and 20 wt .-% of an adduct of 3 moles of ethylene oxide with C 10/12 fatty alcohol. A degreasing process based on such a mixture, however, cannot satisfy on the one hand because of the abundance of the auxiliary substances required. In addition, the use of anionic surfactants and the use of solvents must be largely avoided in the course of ever-increasing environmental awareness.
FR-A-2 303 850 beschreibt oberflächenaktive Mischungen auf Basis von Gemischen ethoxylierter Fettalkohole. Als Verwendungszweck wird der Einsatz in Detergentien genannt.FR-A-2 303 850 describes surface-active mixtures based on mixtures of ethoxylated fatty alcohols. Use in detergents is mentioned as the intended use.
GB-A-2 011 944 beschreibt Flüssigwaschmittel mit einem Gehalt an einer ternären Mischung nichtionischer Tenside, wobei es sich bei diesen Tensiden um hoch-, mittel- und niedrigethoxylierten Fettalkohole handelt.GB-A-2 011 944 describes liquid detergents containing a ternary mixture of nonionic surfactants, these surfactants being high, medium and low ethoxylated fatty alcohols.
Das Anforderungsprofil, das an Arbeitsmittel der erfindungsgemäß betroffenen Art gestellt wird, beschränkt sich jedoch nicht auf das geforderte hervorragende Emulgier- und Dispergiervermögen für Fette, Fettsäuren, Metallseifen und/oder Wachse sowie Schmutzreste aller Art, es sind vielmehr eine Vielzahl weiterer Forderungen zu erfüllen. Das Hilfsmittel muß seinerseits leicht aus der Hautsubstanz auswaschbar sein, es sollen keine unerwünschten Interaktionen mit anderen anionischen, kationischen und/oder nichtionischen Arbeitsmitteln, beispielsweise Farbstoffen und Fettungsmitteln, auftreten. Die angestrebten Entfettungsmittel sollen eine hinreichende Elektrolytbeständigkeit und dabei insbesondere Beständigkeit gegenüber der Wasserhärte auch bei hohen Graden der Wasserhärte aufweisen. Schließlich soll auch die Anwendbarkeit sowohl im sauren wie im alkalischen pH-Bereich gewährleistet sein.The profile of requirements placed on work equipment of the type concerned according to the invention is, however, not limited to the required excellent emulsifying and dispersing capacity for fats, fatty acids, metal soaps and / or waxes as well as dirt residues of all kinds; rather, a large number of further requirements have to be met. For its part, the aid must be easy to wash out of the skin substance, and there should be no undesired interactions with other anionic, cationic and / or nonionic agents, for example dyes and fatliquoring agents. The desired degreasing agents should have sufficient resistance to electrolytes and, in particular, resistance to water hardness even at high levels of water hardness. Finally, the applicability should be guaranteed both in the acidic and in the alkaline pH range.
Die Lehre der Erfindung geht von der Aufgabe aus, im Rahmen der hier angesprochenen Entfettungsmittel auf Basis von nichtionischen Fettalkoholalkoxylaten ein optimiertes Entfettungsmittel zu entwickeln, das eine breite Anwendbarkeit auf unterschiedlichste Einsatzbedingungen bei gleichzeitig optimierten Verfahrensergebnissen gewährleistet.The teaching of the invention is based on the object, in the context of the degreasing agents mentioned here based on nonionic fatty alcohol alkoxylates To develop an optimized degreasing agent that guarantees broad applicability to a wide variety of operating conditions with simultaneously optimized process results.
Die Lösung dieser erfindungsgemäßen Aufgabenstellung liegt in der gezielten Auswahl und Abmischung unterschiedlicher Wirkstoffkomponenten, die sich jedoch insgesamt konstituionell einer Stoffklasse zuordnen lassen, die biologisch optimal verträglich ist.The solution to this problem according to the invention lies in the targeted selection and mixing of different active ingredient components, which, however, can overall be assigned to a substance class that is biologically optimally compatible.
Gegenstand der Erfindung ist die Verwendung von Gemischen nichtionischer Emulgatoren vom Typ der Fettalkoholethoxylate zur Entfettung von Häuten, Blößen, Fellen, Ledern. Dabei sind diese Gemische dadurch charakterisiert, daß sie enthalten
- (a) C12-18-Fettalkohol-Ethoxylate mit im Mittel mehr als 6 EO-Gruppen im Molekül und
- (b) Vorlauf-Fettalkohol-Ethoxylate mit nicht mehr als 3 E0-Gruppen im Molekül,
- i) die den Komponenten (a) und (b) zugrundeliegenden Fettalkohole eine Jodzahl unterhalb von 20 aufweisen und
- ii) die Komponente (b) in einer Menge von etwa 2 bis 20 Gew.-% - bezogen auf die Summe von (a) und (b) - enthalten ist.
- (a) C 12-18 fatty alcohol ethoxylates with an average of more than 6 EO groups in the molecule and
- (b) forerunner fatty alcohol ethoxylates with no more than 3 E0 groups in the molecule,
- i) the fatty alcohols on which components (a) and (b) are based have an iodine number below 20 and
- ii) component (b) is present in an amount of approximately 2 to 20% by weight, based on the sum of (a) and (b).
Der Kern der erfindungsgemäßen Lehre liegt damit im gemeinsamen Einsatz ausgewählter mittel- bis langkettiger Fettalkohol-Ethoxylate - Stoffklasse (a) - und nichtionischen E0-Verbindungen - Stoffklasse (b) -, die sich von den sogenannten Vorlauf-Fettalkoholen ableiten.The essence of the teaching according to the invention thus lies in the joint use of selected medium- to long-chain fatty alcohol ethoxylates - substance class (a) - and nonionic E0 compounds - substance class (b) - which are derived from the so-called preliminary fatty alcohols.
Bei den sogenannten Vorlauf-Fettalkoholen handelt es sich bekanntlich um bevorzugt geradkettige Vertreter des Bereiches unterhalb C12, insbesondere des Bereiches von etwa C6-10. Besondere Bedeutung kommt dabei im Sinne der erfindungsgemäßen Lehre hier dem C8-Vorlauf-Fettalkohol und/oder seinen Abmischungen mit C10-Vorlauf-Fettalkoholen zu.As is known, the so-called preliminary fatty alcohols are preferably straight-chain representatives of the range below C 12 , in particular the range of approximately C 6-10 . Special meaning comes here in the sense of the teaching according to the invention the C 8 pre-fatty alcohol and / or its mixtures with C 10 pre-fatty alcohols.
Sowohl in der Stoffklasse (a) als in der Stoffklasse (b) werden im Rahmen der erfindungsgemäßen Lehre Ethoxylate von Alkoholen der angegebenen Bereiche von C-Zahlen verwendet, die eine Jodzahl unterhalb von 20 aufweisen. Die Wahl der Methode zur Bestimmung der Jodzahl ist dabei an sich von untergeordneter Bedeutung. Im Sinne der vorliegenden Erfindung wird jedoch ausdrücklich auf die Methoden nach Hanus bzw. Wijs, die seit langem Bestandteil der Abteilung C-V der "DGF-Einheitsmethoden" sind, sowie die dazu äquivalente neuere Methode nach Fiebig bezug genommen (vergl. Fat Sci. Technol. 1991, Nr.1, S.13-19).Both in substance class (a) and in substance class (b), ethoxylates of alcohols of the specified ranges of C numbers, which have an iodine number below 20, are used in the context of the teaching according to the invention. The choice of the method for determining the iodine number is of minor importance. For the purposes of the present invention, however, express reference is made to the methods according to Hanus or Wijs, which have long been a part of the CV section of the "DGF standard methods", and to the equivalent newer method according to Fiebig (see Fat Sci. Technol. 1991, No. 1, pp. 13-19).
Ganz besonders bevorzugt werden im Sinne der vorliegenden Erfindung solche Vertreter der Stoffklassen (a) und (b) eingesetzt, bei denen die Jodzahl des zugrundeliegenden Fettalkohols unterhalb von 5 und insbesondere unterhalb von 3 liegt. Durch das Merkmal der Jodzahl soll dabei verdeutlicht werden, daß sich die Lehre der vorliegenden Erfindung auf Mischungen solcher Vertreter der Stoffklassen (a) und (b) richtet, bei denen die zugrundeliegenden Fettalkohole überwiegend gesättigt sind.For the purposes of the present invention, those representatives of substance classes (a) and (b) in which the iodine number of the underlying fatty alcohol is below 5 and in particular below 3 are very particularly preferably used. The characteristic of the iodine number is intended to make it clear that the teaching of the present invention is directed to mixtures of such representatives of the substance classes (a) and (b) in which the underlying fatty alcohols are predominantly saturated.
Dabei kommt bei den den Komponenten (a) und (b) zugrundeliegenden Alkoholen denjenigen besondere Bedeutung zu, die natürlichen Ursprungs sind. Die entsprechenden Alkohole pflanzlichen und/oder tierischen Ursprungs werden bekanntlich aus den zugehörigen Fettsäuren pflanzlichen und/oder tierischen Ursprungs durch Hydrierung gewonnen. Es handelt sich dabei wenigstens weit überwiegend um Alkohole beziehungsweise Alkoholgemische mit gerader C-Zahl. Für den Einsatz im Rahmen der Komponente (a) sind damit besonders geeignet Ethoxylate der entsprechend geradkettigen und gesättigten C12-, C14-, C16- und C18-Alkohole. Gemische dieser Alkoholtypen sind als Grundkörper für die Ethoxylate gemäß (a) bevorzugt. Der wichtigste Alkoholrest für die Komponente zu (b) ist der C8-Vorlauf-Fettalkohol.In the case of the alcohols on which components (a) and (b) are based, those which are of natural origin are of particular importance. The corresponding alcohols of plant and / or animal origin are known to be obtained from the associated fatty acids of plant and / or animal origin by hydrogenation. These are at least largely predominantly alcohols or alcohol mixtures with an even C number. For use in the context of component (a), ethoxylates of the corresponding straight-chain and saturated C 12 -, C 14 , C 16 and C 18 alcohols. Mixtures of these types of alcohol are preferred as the base for the ethoxylates according to (a). The most important alcohol residue for the component to (b) is the C 8 pre-fatty alcohol.
Die als wirkungsvolle Fettemulgatoren ausgewählte Komponente (a) macht die größere Menge des erfindungsgemäßen Entfettungsmittels auf Basis der Mischung von (a) und (b) aus. Die untergeordnete Menge der Komponente (b) liegt im Bereich von 2 bis 25 Gew.-% - bezogen auf die Summe von (a) und (b). Besonders bevorzugt ist dabei der Bereich von 5 bis 22 Gew.-%.Component (a) selected as effective fat emulsifiers makes up the larger amount of the degreasing agent according to the invention based on the mixture of (a) and (b). The minor amount of component (b) is in the range from 2 to 25% by weight, based on the sum of (a) and (b). The range from 5 to 22% by weight is particularly preferred.
Diese Wirkstoffkomponente (b) erfüllt im Rahmen der erfindungsgemäßen Lehre eine wichtige Funktion insbesondere als Dispergierhilfsmittel zur erleichterten Aufnahme und Emulgierung der Fette, Wachse und dergleichen durch die Hauptwirkstoffkomponenten der Stoffklasse (a) im Sinne der erfindungsgemäßen Lehre. Die kombinierte Anwendung von überwiegenden Mengen der Emulgatoren (a) und untergeordneten Mengen der Dispergatoren (b) ist entscheidend für das erfindungsgemäß angestrebte und erreichte verbesserte Arbeitsergebnis.In the context of the teaching according to the invention, this active ingredient component (b) fulfills an important function, in particular as a dispersing aid for facilitating the absorption and emulsification of fats, waxes and the like by the main active ingredient components of substance class (a) within the meaning of the teaching according to the invention. The combined use of predominant amounts of the emulsifiers (a) and minor amounts of the dispersants (b) is decisive for the improved work result sought and achieved according to the invention.
In einer bevorzugten Ausführungsform werden dabei diese Zielvorstellungen durch eine bestimmte Auswahl auch der Komponenten (a) weiter gefördert. Die Erfindung sieht hier vor, als Komponente (a) Mischungen von Fettalkohol-Ethoxylaten unterschiedlicher mittlerer E0-Grade einzusetzen. Vorzugsweise wird dabei der Bereich im Mittel bis 15 E0-Einheiten pro Molekül des Fettalkohols nicht überschritten.In a preferred embodiment, these objectives are further promoted by a specific selection of components (a). Here, the invention provides that mixtures of fatty alcohol ethoxylates of different average E0 grades are used as component (a). The range of up to 15 E0 units per molecule of the fatty alcohol is preferably not exceeded.
In einer wichtigen Ausführungsform werden in der Klasse der Komponenten (a) Gemische aus den nachfolgenden Unterklassen (al) und (a2) eingesetzt:
- (a1):
- Gesättigte C12-18-Fettalkohol-Ethoxylate mit einem mittleren E0-Grad von 6 bis 10, insbesondere 6 bis 8
- (a2):
- C12-18-Fettalkohol-Ethoxylate mit einem mittleren E0-Grad von 9 bis 15, insbesondere 9 bis 12.
- (a1):
- Saturated C 12-18 fatty alcohol ethoxylates with an average E0 degree of 6 to 10, in particular 6 to 8
- (a2):
- C 12-18 fatty alcohol ethoxylates with an average E0 degree of 9 to 15, in particular 9 to 12.
Es hat sich dabei als zweckmäßig erwiesen, im Rahmen dieser Unterkombination von Emulgatoren der Stoffklasse (a) die Komponenten der Unterklasse (al) in größeren Mengen im Vergleich zu den entsprechenden Emulgatoren der Unterklasse (a2) zu verwenden. Vorzugsweise werden die Komponenten (al) und (a2) in Mischungsverhältnissen von wenigstens 2:1 eingesetzt.It has proven to be expedient in this sub-combination of emulsifiers of substance class (a) to use the components of sub-class (al) in larger amounts compared to the corresponding emulsifiers of sub-class (a2). Components (a1) and (a2) are preferably used in mixing ratios of at least 2: 1.
Der mittlere Ethoxylierungsgrad der Komponenten (b) ist - in Anpassung an die kürzere Kettenlänge der hier vorliegenden alkoholischen Grundkomponente - deutlich niedriger als in den Emulgatorkomponenten (al) und/oder (a2). Vorzugsweise werden als Dispergatorkomponente (b) C8-Vorlauf-Fettalkohol-Ethoxylate eines mittleren Ethoxylierungsgrades von 1,5 bis 2,5 eingesetzt.The average degree of ethoxylation of components (b) - in adaptation to the shorter chain length of the alcoholic basic component present here - is significantly lower than in the emulsifier components (al) and / or (a2). Preferably C 8 precursor fatty alcohol ethoxylates having an average degree of ethoxylation of 1.5 to 2.5 are used as dispersant component (b).
Besonders geeignete Wirkstoffgemische im Sinne der erfindungsgemäßen Lehre enthalten beispielsweise 55 bis 70 Gew.-% der Emulgatorkomponente (al) zusammen mit 20 bis 30 Gew.-% der Emulgatorkomponente (a2) neben untergeordneten Mengen der Dispergatorkomponente (b). Wie bereits angegeben beträgt die Untergrenze für die Wirkstoffkomponenten (b) etwa 2 Gew.-% - bezogen auf die Summe der Komponenten (a) und (b) - wobei vorzugsweise aber wenigstens 5 Gew.-% der Komponente (b) im Wirkstoffgemisch enthalten sind.Particularly suitable active substance mixtures in the sense of the teaching according to the invention contain, for example, 55 to 70% by weight of the emulsifier component (a1) together with 20 to 30% by weight of the emulsifier component (a2) in addition to minor amounts of the dispersant component (b). As already stated, the lower limit for the active ingredient components (b) is about 2% by weight, based on the sum of components (a) and (b), but preferably at least 5% by weight of component (b) in the active ingredient mixture are.
Es ist von besonderem Vorteil, daß mit den erfindungsgemäß einzusetzenden Gemischen beispielsweise bei der Blößenentfettung auch ohne die Mitverwendung zusätzlicher Lösungsmittel gute Ergebnisse erzielt werden. Die Kombination der dispergierenden und emulgierenden Wirkstoffe wirkt im praktischen Einsatz fettlösend und fettverteilend in Weiche, Äscher sowie allgemein bei der Entfettung. Die Arbeitsvorgänge beispielsweise in Weiche und Äscher werden durch die Verwendung der erfindungsgemäßen Mittel beschleunigt.It is particularly advantageous that, with the mixtures to be used according to the invention, good results are achieved, for example, in the case of lard degreasing, even without the use of additional solvents. The combination of dispersing and emulsifying In practical use, active ingredients have a fat-dissolving and fat-distributing effect in switches, limbers and in general in degreasing. The work processes, for example in the switch and liming, are accelerated by the use of the agents according to the invention.
In einer weiteren bevorzugten Ausführungsform können die erfindungsgemäßen einzusetzenden Gemische weitere spezielle ausgewählte Lösungsmittel enthalten. Wenn auch grundsätzlich alle Lösungsmittel geeignet sind, die zur hinreichenden Lösung, Emulgierung und/oder Dispergierung der Hilfsmittel beziehungsweise der durch ihre Mitwirkung aus der Hautsubstanz aufzunehmenden Fette und Wachse befähigt sind, so sind hier erfindungsgemäß besondere Auswahlkriterien zweckmäßig und bevorzugt:In a further preferred embodiment, the mixtures to be used according to the invention can contain further specially selected solvents. Although basically all solvents are suitable which are capable of adequately dissolving, emulsifying and / or dispersing the auxiliaries or of the fats and waxes to be absorbed from the skin substance by their cooperation, special selection criteria are expedient and preferred here according to the invention:
Lösungsmittel im Sinne der erfindungsgemäßen Anforderungen sind insbesondere entsprechende organische, nicht oder nur beschränkt wassermischbare Flüssigkeiten, die sich durch hinreichend hohe Flammpunkte - gewöhnlich Flammpunkte oberhalb 100°C - auszeichnen. Als bei Raumtemperatur fließfähige Lösungsmittel sind dabei entsprechende organische Komponenten bevorzugt, die ihrerseits biologisch abbaubar sind.Solvents within the meaning of the requirements according to the invention are, in particular, corresponding organic liquids which are immiscible or only water-miscible to a limited extent and which are distinguished by sufficiently high flash points - usually flash points above 100 ° C. Appropriate organic components, which in turn are biodegradable, are preferred as solvents that flow at room temperature.
Als biologisch abbaubare Flüssigphasen können dabei ganz allgemein Carbonsäureester, insbesondere Ester monofunktioneller Carbonsäuren mit einwertigen Alkoholen, hochsiedende Ether, entsprechende und bei Raumtemperatur fließfähige oleophile Alkohole und/oder Kohlensäureester eingesetzt werden. Es kann dabei zweckmäßig sein, insbesondere in der Klasse der Carbonsäureester, Vertreter ungesättigter Komponenten auf der Seite der esterbildenden Carbonsäuren und/oder der esterbildenden Alkohole auszuwählen. Die hier angesprochenen ungesättigten esterbildenden Komponenten sind ihrerseits bevorzugt bei Raumtemperatur noch fließfähige Verbindungen, so daß im Haut- beziehungsweise Ledergefüge zurückbleibende geringe Mengen der Hilfslösungsmittel auf Esterbasis auch nach einer später gegebenenfalls auftretenden Verseifung beziehungsweise Teilverseifung zu keinen unerwünschten Abscheidungen paraffinartigen Charakters führen.As biodegradable liquid phases, carboxylic acid esters, in particular esters of monofunctional carboxylic acids with monohydric alcohols, high-boiling ethers, corresponding oleophilic alcohols and / or carbonic acid esters which are flowable at room temperature can be used quite generally. It may be expedient to select representatives of unsaturated components on the side of the ester-forming carboxylic acids and / or the ester-forming alcohols, in particular in the class of the carboxylic acid esters. The unsaturated ester-forming components mentioned here are in turn preferably compounds which are still flowable at room temperature, so that small amounts of the auxiliary solvents remain in the skin or leather structure on an ester basis, even after a saponification or partial saponification which may occur later, do not lead to any undesired deposition of paraffin-like character.
Die Menge des biologisch abbaubaren Lösungsmittels kann dabei in breiten Grenzen schwanken und beispielsweise 5 bis 95 Gew.-% der Stoffmischung ausmachen. Die Wirkstoffmischung aus den Komponenten zu (a) und (b) macht in solchen lösungsmittelhaltigen Zubereitungsformen bevorzugt etwa 5 bis 90 Gew.-% aus. Besonders geeignet sind entsprechende Lösungen, die 10 bis 60 Gew.-% der Komponenten (a) und (b) in einem biologisch abbaubaren Lösungsmittel beziehungsweise Lösungsmittelgemisch enthalten. Die hier genannten Gewichtsprozent-Angaben beziehen sich jeweils auf das Gesamtprodukt.The amount of biodegradable solvent can vary within wide limits and can, for example, make up 5 to 95% by weight of the mixture of substances. The active ingredient mixture from the components of (a) and (b) preferably makes up about 5 to 90% by weight in such solvent-containing preparation forms. Appropriate solutions which contain 10 to 60% by weight of components (a) and (b) in a biodegradable solvent or solvent mixture are particularly suitable. The weight percentages given here refer to the total product.
Geeignete Hilfslösungsmittel auf Basis ungesättigter Ester sind insbesondere Verbindungen entsprechender olefinisch ungesättigter höherer Fettsäuren, beispielsweise der Ölsäure, mit gegebenenfalls ebenfalls ungesättigten höheren Fettalkoholen, insbesondere dem Oleylalkohol. Beispiele für die Lösungsmittelphase auf Alkoholbasis sind Guerbet-Alkohole, inbesondere des Bereichs bis C20. Die Auswahl von Ethern und inbesondere oleophilen und unter Normalbedingungen fließfähigen Alkoholen kann zu verbesserten Arbeitsergebnissen bezüglich der Hydrolysebeständigkeit des als Hilfsflüssigphase eingesetzten biologisch abbaubaren Lösungsmittels führen.Suitable auxiliary solvents based on unsaturated esters are, in particular, compounds of corresponding olefinically unsaturated higher fatty acids, for example oleic acid, with optionally also unsaturated higher fatty alcohols, in particular oleyl alcohol. Examples of the alcohol-based solvent phase are Guerbet alcohols, especially in the range up to C 20 . The selection of ethers and in particular oleophilic alcohols which are flowable under normal conditions can lead to improved work results with regard to the hydrolysis resistance of the biodegradable solvent used as the auxiliary liquid phase.
Zur Bestimmung der jeweiligen Entfettungswirkung werden gemäß den nachfolgenden Angaben Schaf-Pickelblößen längs der Rückenlinie geteilt. Die rechte und die linke Hälfte werden als zueinander zugehörig gekennzeichnet und dann in getrennten Verfahren die eine Hälfte unter Einsatz der erfindungsgemäßen Entfettungsmittel und die andere Hälfte unter Einsatz vorbekannter Standard- beziehungsweise Vergleichsprodukte aus dem Gebiet der Entfettungsmittel verarbeitet. Dabei wird im einzelnen wie folgt vorgegangen:To determine the respective degreasing effect, sheep pimples are divided along the back line according to the following information. The right and left halves are identified as belonging to one another and then one half is processed in separate processes using the degreasing agents according to the invention and the other half using previously known standard or comparative products from the field of degreasing agents. The individual procedure is as follows:
- Ausgangsmaterial:
- Englische Domestic-Schafpickelblößen
- %-Angabe bezogen auf:
- Pickelgewicht
- Anfangs-pH:
- ca. 1,8
Rechte Hälfte und linke Hälfte zeichnen (am Hals).
Rechte Hälfte wird jeweils mit Versuchsprodukt, linke Hälfte mit Standard- bzw. Vergleichsprodukt gearbeitet.
Wasser
Flotte ablassen
- Starting material:
- English domestic sheep pimples
- % In relation to:
- Pimple weight
- Initial pH:
- about 1.8
Draw the right half and left half (on the neck).
The right half is worked with the test product, the left half with the standard or comparative product.
water
Drain the fleet
Leder über Nacht auf Bock, abwelken, spannen und bei 25°C trocknen. An der DIN-Entnahmestelle Material für die Fettbestimmung ausschneiden und zur Restfettbestimmung geben.Leather overnight on trestle, wilt, tension and dry at 25 ° C. Cut out material for fat determination at the DIN tapping point and add it for residual fat determination.
Die Entfettung wurde dabei in an sich bekannter Weise mit 3 verschiedenen Entfettungsmitteln des Standes der Technik (Versuche a bis c) und im Vergleich dazu mit einem erfindungsgemäß zusammengesetzten biologisch abbaubaren Entfettungsmittel (Versuch d) unter jeweils gleichen Arbeitsbedingungen durchgeführt. Darüber hinaus wird aus dem Vergleich des erfidungsgemäßen Beispiels d) mit Versuch e) deutlich, daß die Menge des Vorlauf-Fettalkohol-Ethoxylats ein kritisches Merkmal ist.The degreasing was carried out in a manner known per se using 3 different degreasing agents of the prior art (experiments a to c) and, in comparison, using a biodegradable degreasing agent composed according to the invention (experiment d) under the same working conditions in each case. In addition, it is clear from the comparison of example d) according to the invention with experiment e) that the amount of the preliminary fatty alcohol ethoxylate is a critical feature.
Die einzelnen Arbeitsergebnisse aus jeweils mehreren Versuchen sind in der nachfolgenden Tabelle 1 zusammengestellt; der Naturfettgehalt der eingesetzten Blößen (d.h. vor Beginn der Entfettung) betrug dabei 23 - 27 Gew.-%.
NP-10: Anlagerungsprodukt von 10 Mol Ethylenoxid an 1 Mol Nonylphenol
Dehydol LS7: Anlagerungsprodukt von 7 Mol Ethylenoxid an 1 Mol C12/14-Fettalkohol (Fa. Henkel/Düsseldorf)
C8-1E0: Anlagerungsprodukt von 1 Mol Ethylenoxid an 1 Mol C8-Fettalkohol (Octanol)
NP-10 : adduct of 10 moles of ethylene oxide with 1 mole of nonylphenol
Dehydol LS7 : adduct of 7 moles of ethylene oxide with 1 mole of C 12/14 fatty alcohol (Henkel / Düsseldorf)
C8-1E0 : adduct of 1 mole of ethylene oxide with 1 mole of C 8 fatty alcohol (octanol)
Claims (8)
- The use of mixtures of nonionic emulsifiers of the fatty alcohol ethoxylate type for degreasing skins, pelts, hides, leathers characterized in that they contain(a) C12-18 fatty alcohol ethoxylates containing on average more than 6 EO groups in the molecule and(b) head-fractionated fatty alcohol ethoxylates containing no more than 3 EO groups in the molecule,with the proviso thati) the fatty alcohols on which components (a) and (b) are based have an iodine value below 20 andii) component (b) is present in a quantity of around 2 to 25% by weight, based on the sum of (a) and (b).
- The use claimed in claim 1, in which component (a) contains mixtures of fatty alcohol ethoxylates differing in their average EO degrees, the range up to 15 EO and, more particularly, up to 10 EO per mole of fatty alcohol preferably not being exceeded.
- The use claimed in claim 1 or 2, in which component (b) is a head-fractionated C8 fatty alcohol ethoxylate with an average EO degree of 1.5 to 2.5.
- The use claimed in any of claims 1 to 3, in which component (a) is a mixture of(a1): saturated C12-18 fatty alcohol ethoxylates with an average EO degree of 6 to 8 and(a2): those with an average EO degree of around 9 to 12,the mixing ratio between components (a1) and (a2) preferably being 2:1.
- The use claimed in any of claims 1 to 4, characterized in that components (a) and (b) are dissolved in biodegradable solvents based on high-boiling carboxylic acid esters, ethers, alcohols and/or carbonic acid esters liquid at room temperature.
- The use claimed in claim 5, characterized in that components (a) and (b) are present in the biodegradable solvents in quantities of 5 to 90% by weight and preferably in quantities of around 10 to 60% by weight, based on the product as a whole.
- The use claimed in claim 5 or 6, characterized in that Guerbet alcohols and/or higher olefinically unsaturated fatty alcohols are present as the solvents.
- Degreasing preparations based on nonionic emulsifiers of the fatty alcohol alkoxylate type for the treatment of skins, pelts, hides, leathers, characterized in that they contain a mixture of(a) C12-18 fatty alcohol ethoxylates containing on average more than 6 EO groups in the molecule and(b) head-fractionated fatty alcohol ethoxylates containing no more than 3 EO groups in the molecule,with the proviso thati) the fatty alcohols on which components (a) and (b) are based have an iodine value below 20 andii) component (b) is present in a quantity of around 2 to 25% by weight, based on the sum of (a) and (b)and with the further proviso thatiii) component (b) is a head-fractionated C8 fatty alcohol ethoxylate with an average EO degree of 1.5 to 2.5 and/oriv) component (a) is a mixture of(a1): saturated C12-18 fatty alcohol ethoxylates with an average EO degree of 6 to 8 and(a2): those with an average EO degree of around 9 to 12, the mixing ratio between components (a1) and (a2) preferably being 2:1, and/orv) components (a) and (b) being present in the form of a solution in biodegradable solvents based on high-boiling carboxylic acid esters, ethers, alcohols and/or carbonic acid esters liquid at room temperature,- components (a) and (b) being present in a quantity of 5 to 90% by weight and preferably in quantity of around 10 to 60% by weight, based on the product as a whole, in the biodegradable solvents and/or- Guerbet alcohols and/or higher olefinically unsaturated fatty alcohols being present as the solvents.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4207806 | 1992-03-12 | ||
| DE4207806A DE4207806A1 (en) | 1992-03-12 | 1992-03-12 | Biodegradable degreasing agent for skins, hides, pelts and leather - contg. major amt. of satd. fatty alcohol ethoxylate(s) and minor amt. of short chain fatty alcohol ethoxylate(s) with low deg. of ethoxylation |
| DE4301553 | 1993-01-21 | ||
| DE4301553A DE4301553A1 (en) | 1993-01-21 | 1993-01-21 | Degreasing agent for skins and leather |
| PCT/EP1993/000527 WO1993018188A1 (en) | 1992-03-12 | 1993-03-09 | Degreasing agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0630415A1 EP0630415A1 (en) | 1994-12-28 |
| EP0630415B1 true EP0630415B1 (en) | 1996-09-04 |
Family
ID=25912708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93906493A Expired - Lifetime EP0630415B1 (en) | 1992-03-12 | 1993-03-09 | Degreasing agents |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5525120A (en) |
| EP (1) | EP0630415B1 (en) |
| AT (1) | ATE142277T1 (en) |
| BR (1) | BR9306062A (en) |
| DE (1) | DE59303668D1 (en) |
| ES (1) | ES2090985T3 (en) |
| WO (1) | WO1993018188A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104480233A (en) * | 2014-11-10 | 2015-04-01 | 北京泛博化学股份有限公司 | Safety environmental-friendly water-emulsified drum degreasing agent, and preparation method and applications thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4311113A1 (en) * | 1993-04-05 | 1994-10-06 | Henkel Kgaa | Degreasing agent |
| DE10134441A1 (en) * | 2001-07-20 | 2003-02-06 | Basf Ag | Leather degreasing |
| BR0309548B1 (en) | 2002-04-26 | 2013-11-12 | Alkoxylate mixture, process for preparing it, washing or cleaning agent, and use thereof | |
| DE10249077A1 (en) * | 2002-10-21 | 2004-04-29 | Basf Ag | Process for the production of leather |
| DE10358534A1 (en) * | 2003-12-13 | 2005-07-14 | Henkel Kgaa | Adhesion inhibition of microorganisms by nonionic surfactants |
| BRPI0414417B1 (en) * | 2003-12-17 | 2014-11-25 | Akzo Nobel Nv | "Process for degreasing and / or drying of animal fur". |
| DE102012200673A1 (en) * | 2012-01-18 | 2013-07-18 | Henkel Ag & Co. Kgaa | Washing, cleaning or pretreatment agent with increased cleaning power |
| ITFI20120276A1 (en) * | 2012-12-10 | 2014-06-11 | Colortex S P A | NEW PROCESS AND COMPOSITIONS FOR LEATHER DEGREASING |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE759631C (en) * | 1940-08-14 | 1953-05-18 | Ig Farbenindustrie Ag | Process for degreasing hides and skins |
| BE557625A (en) * | 1956-08-13 | |||
| FR2303850A1 (en) * | 1975-03-10 | 1976-10-08 | Rhone Poulenc Ind | Surfactant compsns. contg. ethoxylated alcohols - with the lower alcohol having lower ethoxylation degree than the higher alcohol |
| US3991543A (en) * | 1975-04-21 | 1976-11-16 | Continental Can Company, Inc. | Sealing unit for autoclave sterilization of flexible packages |
| DE2522902C3 (en) * | 1975-05-23 | 1979-12-13 | Chemische Fabrik Stockhausen & Cie, 4150 Krefeld | Process for the simultaneous softening, cleaning and degreasing of raw fumes |
| GB2011944B (en) * | 1978-01-09 | 1982-06-09 | Unilever Ltd | Liquid detergent composition |
| DE2939810A1 (en) * | 1979-10-01 | 1981-04-16 | Henkel KGaA, 4000 Düsseldorf | SPRAY CLEANER SUITABLE FOR TEXTILE TREATMENT |
| DE4009805C1 (en) * | 1990-03-27 | 1991-12-05 | Dr. Th. Boehme Kg Chem. Fabrik Gmbh & Co, 8192 Geretsried, De | |
| DE4029777A1 (en) * | 1990-09-20 | 1992-03-26 | Henkel Kgaa | LIQUID, NON-TENSID COMBINATION WITH IMPROVED CELL TESTABILITY |
| US5246147A (en) * | 1992-05-20 | 1993-09-21 | Sil Medics Ltd. | Liquid material dispenser |
-
1993
- 1993-03-09 BR BR9306062A patent/BR9306062A/en unknown
- 1993-03-09 DE DE59303668T patent/DE59303668D1/en not_active Expired - Fee Related
- 1993-03-09 EP EP93906493A patent/EP0630415B1/en not_active Expired - Lifetime
- 1993-03-09 US US08/302,729 patent/US5525120A/en not_active Expired - Fee Related
- 1993-03-09 ES ES93906493T patent/ES2090985T3/en not_active Expired - Lifetime
- 1993-03-09 AT AT93906493T patent/ATE142277T1/en not_active IP Right Cessation
- 1993-03-09 WO PCT/EP1993/000527 patent/WO1993018188A1/en active IP Right Grant
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104480233A (en) * | 2014-11-10 | 2015-04-01 | 北京泛博化学股份有限公司 | Safety environmental-friendly water-emulsified drum degreasing agent, and preparation method and applications thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2090985T3 (en) | 1996-10-16 |
| WO1993018188A1 (en) | 1993-09-16 |
| EP0630415A1 (en) | 1994-12-28 |
| DE59303668D1 (en) | 1996-10-10 |
| BR9306062A (en) | 1997-11-18 |
| US5525120A (en) | 1996-06-11 |
| ATE142277T1 (en) | 1996-09-15 |
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