EP0651828B1 - Use of guerbet alcohols to prevent the formation of fatty spew on leather - Google Patents
Use of guerbet alcohols to prevent the formation of fatty spew on leather Download PDFInfo
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- EP0651828B1 EP0651828B1 EP93915869A EP93915869A EP0651828B1 EP 0651828 B1 EP0651828 B1 EP 0651828B1 EP 93915869 A EP93915869 A EP 93915869A EP 93915869 A EP93915869 A EP 93915869A EP 0651828 B1 EP0651828 B1 EP 0651828B1
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- leather
- fat
- guerbet alcohols
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- pour point
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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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
Definitions
- the invention relates to the use of special nonionic organic dialkyl compounds to prevent fat rash on leather.
- greasing agents are the most important tools to shape the character of leather.
- the effect of the fatliquor comes from a fiber-insulating lubrication and a hydrophobization.
- the mutual friction is reduced and consequently the suppleness and stretchability of the fabric are improved.
- This has positive effects on the tensile strength of the leather, because in a stretchable material, many fibers align in the direction of tension when subjected to tensile stress and then offer greater resistance to tearing than the same fibers within a brittle material.
- Vegetable and animal oils, fats and waxes are generally used as leather greasing agents, furthermore the hydrolysis, sulfation, oxidation and hardening products obtained from these substances by chemical conversion and finally mineral greasing agents; in detail:
- the saponifiable fats and oils as well as the natural waxes and resins are among the esters.
- oils and fats are the leather specialist Designated esters of glycerin and fatty acids that are solid or liquid at room temperature.
- the leather specialist Designated esters of glycerin and fatty acids that are solid or liquid at room temperature.
- the fatty acids are esterified with higher molecular weight alcohols instead of glycerin.
- waxes are beeswax, Chinese wax, carnauba wax, montan wax and wool fat;
- the most important resins include rosin, yeast oil and shellac.
- the chemical conversion of vegetable and animal fats gives products that are water-soluble and, in addition, have different emulsifying effects on water-insoluble fats.
- the sulfated water-soluble oils of various types are known, the tears modified by oxidation, which are known as dégras or moellon, the soaps that are formed during the hydrolytic splitting of natural fats, hardened fats and finally free fatty acids such as stearic acid as stoving fats.
- Most animal and vegetable fats have a certain affinity for the leather substance, which is considerably increased by the introduction or exposure of hydrophilic groups.
- Mineral greasing agents are also important for leather production. These hydrocarbons are similar to natural fats and oils in some properties, but cannot be saponified. These are fractions from petroleum distillation, which are called mineral oil in liquid form, petroleum jelly in pasty form and paraffin in solid form.
- Fat mixtures used to grease leather tend to develop a rash if they contain a lot of free fatty acids.
- Free fatty acids generally have a higher melting point than their glycerides.
- the hydrolytic cleavage of fatty substances during the storage of the leather increases the risk of fat rashes (cf. B. Kohnstein, Collegium 1913 , 68; W. Fahrion, Chem. Umschau 1917 , 29), but such fat rashes by no means only need to be free To consist of fatty acids.
- Oxy fatty acids can also give rise to fat rashes (C. R think, Collegium 1926 , 419).
- Soaps and licker greases are split in chrome leather, especially in insufficiently deacidified chrome leather, with the release of fatty acids. Sulphated oils and fats show a different tendency to form fat rashes, the tendency to rash generally decreases with a longer lifespan (A.Pankhurst, RGMitton, RFInnes, N.Johnson, Journal of International Society of Leather Trades Chemists 1952 , 379).
- Fat rashes are more likely to occur the more the leather contains fat substances that tend to form rashes.
- the amount, composition and location of the fat mixture of natural fat and lickerfat present in the leather are decisive for the extent and composition of the rash (see O.Grimm, ⁇ sterr. Lederzeitung 1954 , 253).
- Loosely structured leather is less prone to rash than leather with a dense fiber structure.
- Grease rashes are observed more often at low temperatures than at warmer outside temperatures.
- the crystalline fat rashes develop in the hair holes and gland canals, whereby small crystals are initially formed in the depth, which gradually fill the entire hair hole as larger fat crystals, swell beyond the leather surface and matted into a dense crystal film. All fats that contain stearin or palmitin derivatives can cause crystalline fat rashes, with increasing Concentration increases the risk of a rash (see O. Hagen, Switzerland. Ledertechn. Rundsch. 1949 , 1).
- neutral fats i.e. substances suitable for leather greasing which do not contain any ionic groups in the molecule, e.g. Fats, waxes and hydrocarbons to form fat rashes.
- Those neutral fats which represent stearin and / or palmitin derivatives, e.g. corresponding triglycerides.
- Neutral greases are of particular importance in the so-called licker process of chrome-tanned leather.
- a licker usually contains about 20 to 40% by weight of an emulsifier and 60 to 80% by weight of a neutral fat. It is a widespread practice in the leather processing industry to use neutral greases for greasing the tanned leather which can be sulfated in a simple manner.
- reaction mixture obtained can be used directly as a licker since it contains an emulsifier in the form of the sulfated triglyceride and the neutral fat in the form of the unreacted triglyceride.
- a triglyceride is reacted with a minor amount of concentrated sulfuric acid or oleum
- the reaction mixture obtained can be used directly as a licker since it contains an emulsifier in the form of the sulfated triglyceride and the neutral fat in the form of the unreacted triglyceride.
- Skin fat consists of a mixture of differently structured lipids, the type and proportions of which are summarized in Table 1 for some important animal species (cf. Martin Hollstein, "Leather library; Volume 4: degreasing, greasing and waterproofing in leather production”; p. 116- 136).
- Scheme 1 shows that the triglycerides represent the most important group of skin lipids in terms of quantity.
- these triglycerides In connection with the formation of fat rash, it is particularly critical from the point of view of the leather technician that these triglycerides are predominantly based on saturated fatty acids: lauric, myristic, palmitic and stearic acid are typical components of this group.
- the wax esters also contain as Components include these fatty acids, which are particularly critical with regard to their tendency to fat rash.
- Scheme 1 Composition of the total lipids of the skin of various animal species (in% based on the total lipid of fresh skin)
- Fat rashes which can be clearly distinguished from mineral rashes by their disappearance when heated with a burning match, can be removed, for example, by rubbing the leather with a cloth soaked in petrol; In order to prevent a rash from developing again, it has been recommended to oil the scars with a neutral mineral oil (cf. F. Stather, "Tanning chemistry and tanning technology", Berlin 1967 , p. 740).
- A.Gluszcak and KJBienkiewicz report on the use of a mixture of wood dust, water, hexane and carbon tetrachloride to remove fat rash (cf. Przegl. Skorzany 1985 , 40 (11-12), 232; cited from Chem. Abstracts 105 (6): 45160e).
- halogenated compounds such as chlorinated hydrocarbons.
- chlorinated paraffins as additives to lipid emulsions to the J.Golonka (Przegl. Skorzany 42 (2), 35; cited from Chem. Abstracts 107 (18): 156865z) describes how to prevent rash formation on chrome-tanned pig fields.
- the present invention therefore relates to the use of Guerbet alcohols to prevent fat rash on leather, one or more Guerbet alcohols of the general formula (I) R1-CH (CH2OH) -R (I) in which the radicals R 1 and R independently of one another represent an alkyl group having 6 to 12 C atoms, with the proviso that the total number of C atoms per alcohol molecule is in the range from 16 to 24, with a pour point below 6 ° C.
- those Guerbet alcohols are used whose pour point is below -10 ° C.
- Guerbet alcohols (I) with a pour point below -10 ° C. are 2-hexyldecan-1-ol and 2-octyldodecan-1-ol for the purposes of the invention.
- the invention further relates to compositions which prevent fat rash and which contain a fatliquor and an additive which prevents fat rash, the additive comprising one or more Guerbet alcohols of the general formula (I) R1-CH (CH2OH) -R (I) in which the radicals R 1 and R independently of one another represent an alkyl group having 6 to 12 C atoms, with the proviso that the total number of C atoms per alcohol molecule is in the range from 16 to 24, with a pour point below 6 ° C.
- the additive comprising one or more Guerbet alcohols of the general formula (I) R1-CH (CH2OH) -R (I) in which the radicals R 1 and R independently of one another represent an alkyl group having 6 to 12 C atoms, with the proviso that the total number of C atoms per alcohol molecule is in the range from 16 to 24, with a pour point below 6 ° C.
- compositions are those in which the fatliquor is a neutral fat.
- Neutral fat is understood in the sense of the nomenclature common in leather technology to mean any greasy and slightly water-soluble substance.
- Examples of neutral oils are triglycerides, alkanes and fatty acids.
- the invention further relates to a process for greasing leather, in which tanned leather is treated with an additive which prevents fat and a fat rash, one or more Guerbet alcohols of the general formula (I) being used as the additive.
- R1-CH (CH2OH) -R (I) in which the radicals R 1 and R independently of one another represent an alkyl group having 6 to 12 C atoms, with the proviso that the total number of C atoms per alcohol molecule is in the range from 16 to 24, with a pour point below 6 ° C.
- a neutral fat is used as the fatliquor.
- the method according to the invention is particularly suitable for greasing chrome-tanned leather.
- Guerbet alcohols of the formula (I) which have a pour point below -10 ° C. are used as additives.
- the greasing process is carried out in a conventional manner.
- the grease must be transported into the capillary spaces between the leather fibers and the fibrils, and fibers and fibrils must be coated with a grease film as evenly as possible.
- the greasing process is always carried out on moist leather, because the leather fibers are separated from one another by water in the moist state. The fat then penetrates slowly, but very evenly into the damp leather.
- the amount of fatty substances deposited in the leather is not subject to any particular restrictions and essentially depends on the particular type of leather.
- vegetable-tanned bottom leather and insole leather contain little fat (approx. 0.5-2%), vegetable-tanned pale leather 15-23%, drive belt leather 5-20%, harness leather and some technical special leather 25% and more.
- Chrome-garment upper leather usually contain only 2-6% fat, chrome-garment leather a little more (4-10%), waterproof leather about 15-21%.
- the practical execution of the leather greasing can be done by simply oiling the wet leather before drying, also by lubricating the wet leather on the board ("cold greasing"), by greasing the wet leather in the halk barrel ("warm greasing"), by baking the dry leather and by treating the wet leather with an aqueous fat emulsion, the so-called fat licker.
- the latter process plays a particularly important role in chrome-tanned leathers. It is therefore the preferred form of leather greasing in the context of the present invention.
- the Guerbet alcohols (I) are prepared by conventional synthetic methods of organic chemistry. In addition, many of them are commercially available.
- the usable proportions of the Guerbet alcohols (I) according to the invention or their mixtures in fatliquoring agents range from 5 to 70% by weight, preferably from 5 to 30% by weight, based on the mixture as a whole.
- the leather pretreated according to No. 2 was tested for its tendency to form fat rashes.
- the method used here is a modification of the method by H.A. Ollert (see "Das Leder" 1989, p. 256).
- the good correlation of the test results with the results of long-term storage indicated by Ollert could be confirmed in our own investigations.
- agents known from the prior art such as chlorinated paraffins, was recorded and confirmed in the test.
- the leather to be tested (pretreated according to No. 2) was punched out in a circle - without conditioning - (diameter: 155 mm).
- the leather washers were then used to cover the opening of a 1 liter flat ground cup filled with 300 ml of tap water (outside diameter: 155 mm), with the grain side on the top (outside).
- the leather was fixed with a tension ring and then the water was heated to boiling and kept at the boiling temperature for 2 minutes. In this way, the pretreated leather was exposed to a defined thermal load, with water vapor escaping from the scars.
- the clamping ring was then removed, the leather disc covering the flat ground cup was removed and the water poured out.
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Abstract
Description
Die Erfindung betrifft die Verwendung spezieller nichtionischer organischer Dialkylverbindungen zur Verhinderung von Fettausschlag auf Leder.The invention relates to the use of special nonionic organic dialkyl compounds to prevent fat rash on leather.
Neben den Gerbstoffen sind Fettungsmittel die wichtigsten Hilfsmittel, um den Charakter von Leder zu prägen. Die Wirkung der Fettungsmittel kommt durch eine faserisolierende Schmierung und durch eine Hydrophobierung zustande. Durch Umhüllung der Lederfasern mit einem Fettfilm wird die gegenseitige Reibung verringert und demzufolge die Geschmeidigkeit und Dehnbarkeit des Gewebes verbessert. Das hat positive Auswirkungen auf die Reißfestigkeit des Leders, denn in einem dehnbaren Werkstoff richten sich viele Fasern bei Zugbeanspruchung in der Zugrichtung aus und setzen dann dem Zerreißen einen größeren Widerstand entgegen als dieselben Fasern innerhalb eines spröden Werkstoffes.In addition to the tannins, greasing agents are the most important tools to shape the character of leather. The effect of the fatliquor comes from a fiber-insulating lubrication and a hydrophobization. By covering the leather fibers with a grease film, the mutual friction is reduced and consequently the suppleness and stretchability of the fabric are improved. This has positive effects on the tensile strength of the leather, because in a stretchable material, many fibers align in the direction of tension when subjected to tensile stress and then offer greater resistance to tearing than the same fibers within a brittle material.
Als Lederfettungsmittel werden im allgemeinen pflanzliche und tierische Öle, Fette und Wachse eingesetzt, ferner die aus diesen Stoffen durch chemische Umwandlung gewonnenen Hydrolyse-, Sulfierungs-, Oxidations- und Härtungsprodukte und schließlich mineralische Fettungsmittel; im einzelnen:Vegetable and animal oils, fats and waxes are generally used as leather greasing agents, furthermore the hydrolysis, sulfation, oxidation and hardening products obtained from these substances by chemical conversion and finally mineral greasing agents; in detail:
Die verseifbaren Fette und Öle sowie die natürlichen Wachse und Harze gehören zu den Estern. Unter Ölen und Fetten werden dabei vom Lederfachmann Ester aus Glycerin und Fettsäuren bezeichnet, die bei Raumtemperatur fest bzw. flüssig sind. Zur Lederfettung werden dabei aus der Gruppe der tierischen Fette insbesondere Trane, Fischöl, Rindertalg und Rinderklauenöl, aus der Gruppe der pflanzlichen Fette Rizinusöl, Rüböl und Leinöl herangezogen. In Wachsen und Harzen sind die Fettsäuren statt mit Glycerin mit höhermolekularen Alkoholen verestert. Beispiele für Wachse sind Bienenwachs, chinesisches Wachs, Carnaubawachs, Montanwachs und Wollfett; zu den wichtigsten Harzen zählen Kolophonium, Juchtenöl und Schellack.The saponifiable fats and oils as well as the natural waxes and resins are among the esters. Among the oils and fats are the leather specialist Designated esters of glycerin and fatty acids that are solid or liquid at room temperature. For leather greasing, from the group of animal fats in particular trane, fish oil, beef tallow and beef claw oil, from the group of vegetable fats castor oil, rape oil and linseed oil are used. In waxes and resins, the fatty acids are esterified with higher molecular weight alcohols instead of glycerin. Examples of waxes are beeswax, Chinese wax, carnauba wax, montan wax and wool fat; The most important resins include rosin, yeast oil and shellac.
Durch chemische Umwandlung pflanzlicher und tierischer Fette erhält man Produkte, die wasserlöslich sind und die darüber hinaus in unterschiedlichem Maße emulgierend auf wasserunlösliche Fettstoffe wirken. Bekannt sind etwa die sulfierten wasserlöslichen Öle verschiedenster Art, die durch Oxidation veränderten Trane, die als Dégras oder Moellon bezeichnet werden, ferner die Seifen, die bei der hydrolytischen Spaltung natürlicher Fette entstehen, gehärtete Fette sowie schließlich freie Fettsäuren wie Stearinsäure als Einbrennfette. Die meisten tierischen und pflanzlichen Fette weisen eine gewisse Affinität zur Ledersubstanz auf, die durch die Einführung oder Freilegung hydrophiler Gruppen noch beträchtlich gesteigert wird.The chemical conversion of vegetable and animal fats gives products that are water-soluble and, in addition, have different emulsifying effects on water-insoluble fats. For example, the sulfated water-soluble oils of various types are known, the tears modified by oxidation, which are known as dégras or moellon, the soaps that are formed during the hydrolytic splitting of natural fats, hardened fats and finally free fatty acids such as stearic acid as stoving fats. Most animal and vegetable fats have a certain affinity for the leather substance, which is considerably increased by the introduction or exposure of hydrophilic groups.
Wichtig für die Lederherstellung sind weiter die mineralischen Fettungsmittel. Diese Kohlenwasserstoffe sind den natürlichen Fetten und Ölen in manchen Eigenschaften ähnlich, lassen sich jedoch nicht verseifen. Es handelt sich um Fraktionen der Erdöldestillation, die in flüssiger Form Mineralöl, in pastöser Form Vaseline und in fester Form Paraffin genannt werden.Mineral greasing agents are also important for leather production. These hydrocarbons are similar to natural fats and oils in some properties, but cannot be saponified. These are fractions from petroleum distillation, which are called mineral oil in liquid form, petroleum jelly in pasty form and paraffin in solid form.
In vielen Fällen bilden sich jedoch auf der Oberfläche der gegerbten und gefetteten Leder im Laufe der Zeit unerwünschte Flecken. Der Fachmann spricht in diesem Falle von "Fettausschlägen" (englisch: fatty spew). Fettausschläge entstehen vornehmlich auf chromgegerbten Ledern nach kürzerer oder längerer Lagerung als weißer, oft schleierartiger Belag, der nur einzelne Stellen oder auch die ganze Lederfläche bedeckt. Der Ausschlag ist auf ein Heraustreten von festen Fettstoffen aus dem Leder zurückzuführen. Er kann durch das an sich im Leder vorhandene Naturfett oder durch Fettstoffe verursacht sein, die erst im Zuge der Lederfettung der Leder einverleibt worden sind.In many cases, however, undesirable stains form on the surface of the tanned and greased leather over time. In this case, the person skilled in the art speaks of "fatty spew". Grease rashes occur primarily on chrome-tanned leather after shorter or longer storage as a white, often veil-like covering that only covers individual areas or the entire leather surface. The rash is due to the emergence of solid fatty substances from the leather. It can be due to the natural fat or in the leather itself be caused by fatty substances that were only incorporated into the leather during the course of leather greasing.
Zum Fetten von Leder benutzte Fettgemische neigen insbesondere dann zur Bildung von Ausschlag, wenn sie viel freie Fettsäuren enthalten. Freie Fettsäuren weisen im allgemeinen einen höheren Schmelzpunkt auf als ihre Glyceride. Die hydrolytische Spaltung von Fettstoffen bei der Lagerung des Leders erhöht entsprechend die Gefahr des Auftretens von Fettausschlägen (vergl. B. Kohnstein, Collegium 1913, 68; W.Fahrion, Chem. Umschau 1917, 29), doch brauchen solche Fettausschläge keineswegs nur aus freien Fettsäuren zu bestehen. Auch Oxyfettsäuren können zu Fettausschlägen Veranlassung geben (C.Rieß, Collegium 1926, 419).Fat mixtures used to grease leather tend to develop a rash if they contain a lot of free fatty acids. Free fatty acids generally have a higher melting point than their glycerides. The hydrolytic cleavage of fatty substances during the storage of the leather increases the risk of fat rashes (cf. B. Kohnstein, Collegium 1913 , 68; W. Fahrion, Chem. Umschau 1917 , 29), but such fat rashes by no means only need to be free To consist of fatty acids. Oxy fatty acids can also give rise to fat rashes (C. Rieß, Collegium 1926 , 419).
Seifen und Lickerfette werden in Chromleder, besonders in nicht genügend entsäuertem Chromleder, unter Freisetzen von Fettsäuren gespalten. Sulfierte Öle und Fette weisen eine unterschiedlich starke Neigung zur Bildung von Fettausschlägen auf, die Ausschlagsneigung geht mit längerer Lebensdauer im allgemeinen zurück (A.Pankhurst, R.G.Mitton, R.F.Innes, N.Johnson, Journal of International Society of Leather Trades Chemists 1952, 379).Soaps and licker greases are split in chrome leather, especially in insufficiently deacidified chrome leather, with the release of fatty acids. Sulphated oils and fats show a different tendency to form fat rashes, the tendency to rash generally decreases with a longer lifespan (A.Pankhurst, RGMitton, RFInnes, N.Johnson, Journal of International Society of Leather Trades Chemists 1952 , 379).
Fettausschläge treten umso leichter auf, je mehr das Leder zur Ausschlagsbildung neigende Fettstoffe enthält. Für den Umfang und die Zusammensetzung des Ausschlags sind Menge, Zusammensetzung und Lage des im Leder vorhandenen Fettgemisches aus Naturfett und Lickerfett maßgebend (vergl. O.Grimm, Österr. Lederzeitung 1954, 253). Locker strukturiertes Leder neigt weniger zur Ausschlagsbildung als Leder mit dichtem Fasergefüge. Fettausschläge werden bei niedrigen Temperaturen häufiger beobachtet als bei wärmeren Außentemperaturen.Fat rashes are more likely to occur the more the leather contains fat substances that tend to form rashes. The amount, composition and location of the fat mixture of natural fat and lickerfat present in the leather are decisive for the extent and composition of the rash (see O.Grimm, Österr. Lederzeitung 1954 , 253). Loosely structured leather is less prone to rash than leather with a dense fiber structure. Grease rashes are observed more often at low temperatures than at warmer outside temperatures.
Die kristallinen Fettausschläge entwickeln sich in den Haarlöchern und Drüsenkanälen, wobei zunächst kleine Kriställchen in der Tiefe gebildet werden, die allmählich als größere Fettkristalle das ganze Haarloch ausfüllen, über die Lederoberfläche hinausquellen und zu einem dichten Kristallfilm verfilzen. Alle Fette, die Stearin- oder Palmitinderivate enthalten, können kristalline Fettausschläge verursachen, mit zunehmender Konzentration wird die Ausschlagsgefahr vergrößert (vergl. O.Hagen, Schweiz. Ledertechn. Rundsch. 1949, 1).The crystalline fat rashes develop in the hair holes and gland canals, whereby small crystals are initially formed in the depth, which gradually fill the entire hair hole as larger fat crystals, swell beyond the leather surface and matted into a dense crystal film. All fats that contain stearin or palmitin derivatives can cause crystalline fat rashes, with increasing Concentration increases the risk of a rash (see O. Hagen, Switzerland. Ledertechn. Rundsch. 1949 , 1).
Insbesondere neigen die sogenannten Neutralfette, d.h. solche zur Lederfettung geeigneten Substanzen, die keine ionischen Gruppen im Molekül enthalten, z.B. Fette, Wachse und Kohlenwasserstoffe, zur Bildung von Fettausschlägen. Besonders kritisch sind dabei diejenigen Neutralfette, die Stearin- und/oder Palmitinderivate darstellen, z.B. entsprechende Triglyceride. Ganz besondere Bedeutung kommt den Neutralfetten bei den sogenannten Licker-Verfahren chromgegerbter Leder zu. Ein Licker enthält üblicherweise etwa 20 bis 40 Gew.-% eines Emulgators und 60 bis 80 Gew.-% eines Neutralfettes. In der lederverarbeitenden Industrie ist es dabei eine weitverbreitete Praxis, solche Neutralfette zum Fetten der gegerbten Leder einzusetzen, die sich in einfacher Weise sulfatieren lassen. Setzt man etwa ein Triglycerid mit einer untergeordneten Menge an konzentrierter Schwefelsäure oder Oleum um, so läßt sich das dabei erhaltene Reaktionsgemisch direkt als Licker verwenden, da es einerseits einen Emulgator in Form des sulfatierten Triglycerids und andererseits das Neutralfett in Form des nicht umgesetzten Triglycerids enthält. In diesem Zusammenhang sei auch ausdrücklich auf den Beispielteil dieser Anmeldung verwiesen.In particular, the so-called neutral fats, i.e. substances suitable for leather greasing which do not contain any ionic groups in the molecule, e.g. Fats, waxes and hydrocarbons to form fat rashes. Those neutral fats which represent stearin and / or palmitin derivatives, e.g. corresponding triglycerides. Neutral greases are of particular importance in the so-called licker process of chrome-tanned leather. A licker usually contains about 20 to 40% by weight of an emulsifier and 60 to 80% by weight of a neutral fat. It is a widespread practice in the leather processing industry to use neutral greases for greasing the tanned leather which can be sulfated in a simple manner. If, for example, a triglyceride is reacted with a minor amount of concentrated sulfuric acid or oleum, the reaction mixture obtained can be used directly as a licker since it contains an emulsifier in the form of the sulfated triglyceride and the neutral fat in the form of the unreacted triglyceride. In this connection, reference is expressly made to the example part of this application.
Neben dem Einsatz von Fettungsmitteln aus der Gruppe der Neutralfette spielen die im Leder bereits vorhandenen Naturfette eine große Rolle für das Auftreten von Fettausschlag.In addition to the use of greasing agents from the group of neutral fats, the natural fats already present in the leather play a major role in the occurrence of fat rashes.
Hautfett besteht aus einer Mischung unterschiedlich aufgebauter Lipide, deren Art und Mengenanteile in Tabelle 1 für einige wichtige Tierarten zusammengestellt ist (vergl. Martin Hollstein, "Bibliothek des Leders; Band 4: Entfetten, Fetten und Hydrophobieren bei der Lederherstellung"; S. 116-136). Schema 1 verdeutlicht, daß die Triglyceride die mengenmäßig bedeutendste Gruppe der Hautlipide darstellen. Dabei ist im Zusammenhang mit der Bildung von Fettausschlag aus der Sicht des Ledertechnikers besonders kritisch, daß diese Triglyceride vorwiegend auf Basis gesättigter Fettsäuren aufgebaut sind: Laurin-, Myristin-, Palmitin- und Stearinsäure sind typische Bausteine dieser Gruppe. Auch die Wachsester enthalten als Bausteine unter anderem diese hinsichtlich Fettausschlagsneigung besonders kritischen Fettsäuren.Skin fat consists of a mixture of differently structured lipids, the type and proportions of which are summarized in Table 1 for some important animal species (cf. Martin Hollstein, "Leather library; Volume 4: degreasing, greasing and waterproofing in leather production"; p. 116- 136). Scheme 1 shows that the triglycerides represent the most important group of skin lipids in terms of quantity. In connection with the formation of fat rash, it is particularly critical from the point of view of the leather technician that these triglycerides are predominantly based on saturated fatty acids: lauric, myristic, palmitic and stearic acid are typical components of this group. The wax esters also contain as Components include these fatty acids, which are particularly critical with regard to their tendency to fat rash.
Die Aussagen von Pfleiderer konnten in eigenen sondierenden Untersuchungen auf geäscherten und gespaltenen Rindernarbenblößen bestätigt werden. In den Bauchteilen wurden dabei Naturfettanteile von bis zu 8% und mehr gefunden.The statements made by Pfleiderer could be confirmed in our own probing investigations on ashes and split beef scars. Natural fat portions of up to 8% and more were found in the abdominal parts.
Leder mit hohem Naturfettgehalt erfordert daher spezielle Maßnahmen, um die Neigung zur Bildung von Fettausschlägen zu unterdrücken. Beispielsweise ist es möglich und in der Praxis durchaus üblich, die Leder entsprechend zu entfetten, was jedoch einen speziellen Arbeitsgang erfordert. Andere Möglichkeiten sind für die Praxis fast bedeutungslos.Leather with a high natural fat content therefore requires special measures to suppress the tendency to form fat rashes. For example, it is possible and quite common in practice, the leather degreasing accordingly, but this requires a special operation. Other options are almost meaningless in practice.
Fettausschläge, die sich durch ihr Verschwinden beim Erwärmen mittels eines brennenden Streichholzes eindeutig von Mineralausschlägen unterscheiden lassen, können z.B. durch Abreiben des Leders mit einem benzingetränkten Lappen entfernt werden; um eine anschließends erneute Bildung von Ausschlag zu verhindern, ist empfohlen worden, den Narben mit einem neutralen Mineralöl abzuölen (vergl. F.Stather, "Gerbereichemie und Gerbereitechnologie", Berlin 1967, S. 740). Über die Verwendung einer Mischung aus Holzstaub, Wasser, Hexan und Tetrachlormethan zur Entfernung von Fettausschlag berichten A.Gluszcak und K.J.Bienkiewicz (vergl. Przegl. Skorzany 1985, 40(11-12), 232; zitiert nach Chem. Abstracts 105(6):45160e).Fat rashes, which can be clearly distinguished from mineral rashes by their disappearance when heated with a burning match, can be removed, for example, by rubbing the leather with a cloth soaked in petrol; In order to prevent a rash from developing again, it has been recommended to oil the scars with a neutral mineral oil (cf. F. Stather, "Tanning chemistry and tanning technology", Berlin 1967 , p. 740). A.Gluszcak and KJBienkiewicz report on the use of a mixture of wood dust, water, hexane and carbon tetrachloride to remove fat rash (cf. Przegl. Skorzany 1985 , 40 (11-12), 232; cited from Chem. Abstracts 105 (6): 45160e).
Die innerhalb eines Zeitraums von zwei bis vier Wochen beobachtete Bildung von Fettausschlag auf handelsüblichem Bekleidungs- und Handschuhleder konnte durch die Verwendung von Glutaraldehyd bei der Gerbung oder durch Verwendung eines Mineralöl-haltigen Lickers verhindert werden (vergl. A.Gluszcak, K.J.Bienkiewicz, Przegl. Skorzany 1985, 40(11-12), 232; zitiert nach Chem. Abstracts 105(6):45160e). Die Methode von Gluszcak und Bienkiewicz hat jedoch den Nachteil, auf eine spezielle Gerbmethode beschränkt zu sein; sie berührt jedoch nicht chromgegerbte Leder, die nach wie vor den weitaus größten Anteil aller Leder des Marktes darstellen.The formation of a fat rash on commercially available clothing and glove leather observed within a period of two to four weeks could be prevented by using glutaraldehyde in the tanning process or by using a mineral oil-containing licker (see A.Gluszcak, KJBienkiewicz, Przegl. Skorzany 1985 , 40 (11-12), 232; cited from Chem. Abstracts 105 (6): 45160e). The Gluszcak and Bienkiewicz method, however, has the disadvantage of being limited to a specific tanning method; however, it does not affect chrome-tanned leather, which is still by far the largest share of all leather on the market.
Da im Zuge der Lederverarbeitung jedoch nach dem Gerben ohnehin als nahezu obligatorischer Arbeitsgang eine Fettung erforderlich ist, um die angestrebten Produkteigenschaften zu erreichen, ist es in der Praxis üblich geworden, mit speziellen synthetischen Fettungsmitteln zu arbeiten, deren Neigung zur Bildung von Fettausschlag gering ist.However, since in the course of leather processing, after tanning, greasing is required as an almost obligatory step in order to achieve the desired product properties, it has become common practice to work with special synthetic greasing agents whose tendency to form a fat rash is low.
Eine in dieser Hinsicht üblicherweise eingesetzte Klasse von Fettungsmitteln sind halogenierte Verbindungen wie Chlorkohlenwasserstoffe. Die steigenden ökologischen und toxikologischen Anfoderungen an Mittel, die in die Umwelt gelangen, bzw. mit denen der Verbraucher in Berührung kommt, machen jedoch diese Substanzklasse zunehmend unattraktiv. Die Verwendung von Chlorparaffinen als Additive zu Fettlicker-Emulsionen, um die Ausschlagsbildung auf chromgegerbtem Schweinelder zu verhindern beschreibt z.B. J.Golonka (Przegl. Skorzany 42(2), 35; zitiert nach Chem. Abstracts 107(18):156865z).One class of fatliquor commonly used in this regard is halogenated compounds such as chlorinated hydrocarbons. However, the increasing ecological and toxicological requirements for agents that get into the environment or with which the consumer comes into contact make this class of substances increasingly unattractive. The use of chlorinated paraffins as additives to lipid emulsions to the J.Golonka (Przegl. Skorzany 42 (2), 35; cited from Chem. Abstracts 107 (18): 156865z) describes how to prevent rash formation on chrome-tanned pig fields.
Die aus dem Stand der Technik bekannten Methoden zur Verhinderung von Fettausschlag vermögen deshalb insgesamt nicht zu befriedigen.The methods known from the prior art for preventing fat rash are therefore unsatisfactory overall.
Aus dem geschilderten Kontext heraus ist klar, daß die Lederindustrie einen ständigen Bedarf an Additiven bzw. Fettungsmitteln hat, die Fettausschlag auf wirksame Weise verhüten und um dadurch die Palette der handelsüblichen Produkte zu ergänzen und flexibel auf die sich ändernden Anforderungen des Marktes reagieren zu können. Insbesondere besteht ein Bedarf an ökologisch bzw. toxikologisch unbedenklichen Additiven und Fettungsmitteln, die bei ihrer Anwendung nicht zu einer unerwünschten Bildung von Fettausschlag führen.From the context described, it is clear that the leather industry has a constant need for additives or greasing agents that effectively prevent fat rashes and thereby supplement the range of commercially available products and be able to react flexibly to the changing demands of the market. In particular, there is a need for ecologically or toxicologically safe additives and fatliquoring agents which, when used, do not lead to an undesirable formation of fat rash.
Es wurde nun gefunden, daß bestimmte Verbindungen der allgemeine Formel (I) die oben genannten Forderungen in jeder Hinsicht ausgezeichnet erfüllen und in vorteilhafter Weise als Fettauschlag verhütende Additive bei der Fettung von Leder eingesetzt werden können.It has now been found that certain compounds of the general formula (I) meet the above-mentioned requirements excellently in all respects and can advantageously be used as additives which prevent fat exchange in leather greasing.
Gegenstand der vorliegenden Erfindung ist daher die Verwendung von Guerbet-Alkoholen zur Verhinderung von Fettausschlag auf Leder, wobei man bei der Fettung von Leder ein oder mehrere Guerbet-Alkohole der allgemeinen Formel (I)
R¹-CH(CH₂OH)-R (I)
worin die Reste R¹ und R unabhängig voneinander eine Alkylgruppe mit 6 bis 12 C-Atomen bedeuten, mit der Maßgabe, daß die Gesamtzahl der C-Atome pro Alkoholmolekül im Bereich von 16 bis 24 liegt,
mit einem Stockpunkt unterhalb von 6 °C einsetzt.The present invention therefore relates to the use of Guerbet alcohols to prevent fat rash on leather, one or more Guerbet alcohols of the general formula (I)
R¹-CH (CH₂OH) -R (I)
in which the radicals R 1 and R independently of one another represent an alkyl group having 6 to 12 C atoms, with the proviso that the total number of C atoms per alcohol molecule is in the range from 16 to 24,
with a pour point below 6 ° C.
In einer bevorzugten Ausführungsform werden diejenigen Guerbet-Alkohole eingesetzt, deren Stockpunkt unterhalb von -10 °C liegt.In a preferred embodiment, those Guerbet alcohols are used whose pour point is below -10 ° C.
Ganz besonders geeignete Guerbet-Alkohole (I) mit einem Stockpunkt unterhalb von -10 °C sind im Sinne der Erfindung 2-Hexyldecan-1-ol und 2-Octyldodecan-1-ol.Very particularly suitable Guerbet alcohols (I) with a pour point below -10 ° C. are 2-hexyldecan-1-ol and 2-octyldodecan-1-ol for the purposes of the invention.
Ein weiterer Gegenstand der Erfindung sind Fettausschlag verhütende Zusammensetzungen enthaltend ein Fettungsmittel und ein Fettausschlag verhütendes Additiv, wobei das Additiv ein oder mehrere Guerbet-Alkohole der allgemeinen Formel (I)
R¹-CH(CH₂OH)-R (I)
worin die Reste R¹ und R unabhängig voneinander eine Alkylgruppe mit 6 bis 12 C-Atomen bedeuten, mit der Maßgabe, daß die Gesamtzahl der C-Atome pro Alkoholmolekül im Bereich von 16 bis 24 liegt,
mit einem Stockpunkt unterhalb von 6 °C umfaßt.The invention further relates to compositions which prevent fat rash and which contain a fatliquor and an additive which prevents fat rash, the additive comprising one or more Guerbet alcohols of the general formula (I)
R¹-CH (CH₂OH) -R (I)
in which the radicals R 1 and R independently of one another represent an alkyl group having 6 to 12 C atoms, with the proviso that the total number of C atoms per alcohol molecule is in the range from 16 to 24,
with a pour point below 6 ° C.
Bevorzugt sind dabei diejenigen Zusammensetzungen, bei denen das Fettungsmittel ein Neutralfett ist. Unter Neutralfett ist dabei im Sinne der in der Ledertechnik üblichen Nomenklatur jede fettende und schwr wasserlösliche Substanz zu verstehen. Beispiele für Neutralöle sind Triglyceride, Alkane und Fettsäuren.Preferred compositions are those in which the fatliquor is a neutral fat. Neutral fat is understood in the sense of the nomenclature common in leather technology to mean any greasy and slightly water-soluble substance. Examples of neutral oils are triglycerides, alkanes and fatty acids.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zum Fetten von Leder, wobei man gegerbtes Leder mit einem Fettungsmittel und einem Fettausschlag verhütenden Additiv behandelt, wobei man als Additiv ein oder mehrere Guerbet-Alkohole der allgemeinen Formel (I)
R¹-CH(CH₂OH)-R (I)
worin die Reste R¹ und R unabhängig voneinander eine Alkylgruppe mit 6 bis 12 C-Atomen bedeuten, mit der Maßgabe, daß die Gesamtzahl der C-Atome pro Alkoholmolekül im Bereich von 16 bis 24 liegt,
mit einem Stockpunkt unterhalb von 6 °C einsetzt.The invention further relates to a process for greasing leather, in which tanned leather is treated with an additive which prevents fat and a fat rash, one or more Guerbet alcohols of the general formula (I) being used as the additive.
R¹-CH (CH₂OH) -R (I)
in which the radicals R 1 and R independently of one another represent an alkyl group having 6 to 12 C atoms, with the proviso that the total number of C atoms per alcohol molecule is in the range from 16 to 24,
with a pour point below 6 ° C.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird als Fettungsmittel ein Neutralfett eingesetzt. Das erfindungsgemäße Verfahren eignet sich insbesondere zur Fettung chromgegerbter Leder.In a preferred embodiment of the method according to the invention, a neutral fat is used as the fatliquor. The method according to the invention is particularly suitable for greasing chrome-tanned leather.
In einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden als Additive solche Guerbet-Alkohole der Formel (I) eingesetzt, die einen Stockpunkt unterhalb von -10 °C aufweisen.In a particularly preferred embodiment of the process according to the invention, Guerbet alcohols of the formula (I) which have a pour point below -10 ° C. are used as additives.
Die praktische Durchführung des Fettungsprozesses geschieht in an sich üblicher Weise. Dabei muß im Zuge des Fettungsprozeßes das Fett in die zwischen den Lederfasern und den Fibrillen liegenden Kapillarräume transportiert werden und Fasern und Fibrillen müssen möglichst gleichmäßig mit einem Fettfilm umhüllt werden. Der Fettungsprozeß wird, abgesehen von der Methode des Einbrennens, stets an feuchtem Leder durchgeführt, weil in feuchtem Zustand die Lederfasern durch Wasser voneinander getrennt sind. Das Fett dringt dann zwar langsam, jedoch sehr gleichmäßig in das feuchte Leder ein.The greasing process is carried out in a conventional manner. In the course of the greasing process, the grease must be transported into the capillary spaces between the leather fibers and the fibrils, and fibers and fibrils must be coated with a grease film as evenly as possible. Apart from the stoving method, the greasing process is always carried out on moist leather, because the leather fibers are separated from one another by water in the moist state. The fat then penetrates slowly, but very evenly into the damp leather.
Die Menge der im Leder abgelagerten Fettstoffe unterliegt an sich keinen besonderen Beschränkungen und richtet sich im wesentlichen nach der jeweiligen Art des Leders. Beispielsweise enthalten pflanzlich gegerbte Bodenleder und Brandsohlenleder nur wenig Fett (ca. 0,5-2%), pflanzlich gegerbte Fahlleder 15-23%, Treibriemenleder 5-20%, Geschirrleder und manche technische Spezialleder 25% und mehr. Chromgare Oberleder enthalten meist nur 2-6% Fett, chromgare Bekleidungsleder etwas mehr (4-10%), Waterproofleder etwa 15-21%.The amount of fatty substances deposited in the leather is not subject to any particular restrictions and essentially depends on the particular type of leather. For example, vegetable-tanned bottom leather and insole leather contain little fat (approx. 0.5-2%), vegetable-tanned pale leather 15-23%, drive belt leather 5-20%, harness leather and some technical special leather 25% and more. Chrome-garment upper leather usually contain only 2-6% fat, chrome-garment leather a little more (4-10%), waterproof leather about 15-21%.
Die praktische Durchführung der Lederfettung kann durch einfaches Abölen des feuchten Leders vor dem Trocknen erfolgen, ferner durch Schmieren des feuchten Leders auf der Tafel ("Kaltfettung"), durch Fetten des feuchten Leders im Halkfaß ("Warmfettung"), durch Einbrennen des trockenen Leders und durch Behandlung des feuchten Leders mit einer wäßrigen Fettemulsion, dem sogenannten Fettlickern. Das letztgenannte Verfahren spielt insbesondere bei chromgegerbten Ledern eine große Rolle. Es ist daher im Rahmen der vorliegenden Erfindung die bevorzugte Form der Lederfettung.The practical execution of the leather greasing can be done by simply oiling the wet leather before drying, also by lubricating the wet leather on the board ("cold greasing"), by greasing the wet leather in the halk barrel ("warm greasing"), by baking the dry leather and by treating the wet leather with an aqueous fat emulsion, the so-called fat licker. The latter process plays a particularly important role in chrome-tanned leathers. It is therefore the preferred form of leather greasing in the context of the present invention.
Die Herstellung der Guerbet-Alkohole (I) erfolgt nach an sich bekannten Syntheseverfahren der organischen Chemie. Sie sind darüber hinaus vielfach kommerziell erhältlich.The Guerbet alcohols (I) are prepared by conventional synthetic methods of organic chemistry. In addition, many of them are commercially available.
Das Ausmaß der Unterdrückung von Fettausschlag durch die Guerbet-Alkohole (I) ist gegenüber dem genannten Stand der Technik originell und neuartig. Die Wirksamkeit der erfindungsgemäßen Verbindungen beruht dabei nicht auf einzelnen Parametern wie etwa dem Stockpunkt, sondern ergibt sich vielmehr erst durch die Kombination aller Merkmale.The extent to which fat rash is suppressed by the Guerbet alcohols (I) is original and novel compared to the prior art mentioned. The effectiveness of the compounds according to the invention is not based on individual parameters such as the pour point, but rather results only from the combination of all features.
Die einsetzbaren Anteile der erfindungsgemäßen Guerbet-Alkohole (I) oder deren Gemische in Fettungsmitteln bewegen sich von 5 bis 70 Gewichtsprozent, bevorzugt von 5 bis 30 Gew.-%, bezogen auf die gesamte Mischung.The usable proportions of the Guerbet alcohols (I) according to the invention or their mixtures in fatliquoring agents range from 5 to 70% by weight, preferably from 5 to 30% by weight, based on the mixture as a whole.
Die folgenden Beispiele sollen den Gegenstand der Erfindung erläutern.The following examples are intended to explain the subject matter of the invention.
Die unter Nr. 2 und Nr.3 beschriebenen Beispiele und Vergleichsbeispiele wurden auf Basis handelsüblicher Produkte durchgeführt, die in Tabelle 1 zusammengestellt sind:
Für sämtliche Versuche wurde chromgegerbtes Rindoberleder (wet-blue) mit einer Stärke von 1,7 mm eingesetzt. Die einzelnen Arbeitsschritte können der Tabelle 2 entnommen werden. Dabei betrug der pH-Wert der Flotte zu Beginn 3,8. Alle %-Angaben der Tabelle 2 beziehen sich auf das Falzgewicht.
Die gemäß Nr.2 vorbehandelten Leder wurden auf ihre Neigung zur Bildung von Fettausschlägen geprüft. Die dabei verwendete Methode ist eine Modifizierung des Verfahrens von H.A.Ollert (vergl. "Das Leder" 1989, S. 256). Die von Ollert angegebene gute Korrelation der Versuchsergebnisse mit den Ergebnissen langfristiger Lagerung konnte in eigenen Untersuchungen bestätigt werden. Insbesondere zeigte sich, daß die gute Wirkung von aus dem Stand der Technik bekannten Mitteln wie Chlorparaffinen in dem Test erfaßt und bestätigt wird.The leather pretreated according to No. 2 was tested for its tendency to form fat rashes. The method used here is a modification of the method by H.A. Ollert (see "Das Leder" 1989, p. 256). The good correlation of the test results with the results of long-term storage indicated by Ollert could be confirmed in our own investigations. In particular, it was found that the good effect of agents known from the prior art, such as chlorinated paraffins, was recorded and confirmed in the test.
Im einzelnen:In detail:
Das jeweils zu prüfende (gemäß Nr.2 vorbehandelten) Leder wurde - ohne zu klimatisieren - kreisförmig ausgestanzt (Durchmesser: 155 mm). Anschließend wurde mit diesen Lederscheiben die Öffnung eines mit 300 ml Leitungswasser gefüllten 1-l-Planschliffbechers (Außendurchiesser: 155 mm) abgedeckt, wobei die Narbenseite oben (außen) lag. Das Leder wurde mit einem Spannring fixiert und anschließend das Wasser zum Sieden erhitzt und 2 Minuten bei Siedetemperatur gehalten. Auf diese Weise wurde das vorbehandelte Leder einer definierten thermischen Belastung ausgesetzt, wobei Wasserdampf aus den Narben austrat. Anschließend wurde der Spannring entfernt, die den Planschliffbecher abdeckende Lederscheibe abgenommen und das Wasser ausgegossen. Die beim Ausgießen des Wassers an den Gefäßwänden haften gebliebenen Wassertropfen wurden dabei im Gefäß belassen, d.h. das Glas wurde nicht zusätzlich getrocknet. Das durch die geschilderte Dampfbehandlung noch feuchte Leder wurde nun unmittelbar in den Planschliffbecher überführt und dieser mit einer Glasscheibe abgedichtet. Die Leder wurden anschließend 5 Tage bei einer Temperatur von 25 °C in dem verschlossenen Becher gelagert. Nach dieser Zeit wurde das Leder visuell auf Fettausschlag geprüft.The leather to be tested (pretreated according to No. 2) was punched out in a circle - without conditioning - (diameter: 155 mm). The leather washers were then used to cover the opening of a 1 liter flat ground cup filled with 300 ml of tap water (outside diameter: 155 mm), with the grain side on the top (outside). The leather was fixed with a tension ring and then the water was heated to boiling and kept at the boiling temperature for 2 minutes. In this way, the pretreated leather was exposed to a defined thermal load, with water vapor escaping from the scars. The clamping ring was then removed, the leather disc covering the flat ground cup was removed and the water poured out. The drops of water stuck to the walls of the vessel when the water was poured out were left in the vessel, i.e. the glass was not additionally dried. The leather, which was still damp due to the steam treatment described, was now transferred directly to the ground cup and sealed with a glass pane. The leathers were then stored in the closed cup at a temperature of 25 ° C. for 5 days. After this time, the leather was visually checked for fat rash.
Die Versuche wurden bezüglich jedes Additivs 10-mal wiederholt. Die Ergebnisse sind in Tabelle 3 zusammengestellt.The experiments were repeated 10 times for each additive. The results are summarized in Table 3.
Es zeigte sich, daß bei Verwendung des reinen Fettungsmittels (Vergleich V1) 80% der Leder Fettausschlag aufwiesen. Die Vergleiche V2 und V3 machen deutlich, daß bei Einsatz nicht erfindungsgemäßer verzweigter Alkohole als Additive die Situation im Sinne einer Vermeidung von Fettausschlägen völlig unbefriedigend ist.It was found that 80% of the leather fat rash was found when using the pure fatliquor (comparison V1). The comparisons V2 and V3 make it clear that when using branched alcohols not according to the invention as Additives the situation in terms of avoiding fat rashes is completely unsatisfactory.
Dagegen waren die Beispiele auf Basis der erfindungsgemäßen Additive (Versuche B1 und B2) frei von Fettausschlägen.
Claims (9)
- The use of Guerbet alcohols for preventing fatty spew on leather, characterized in that one or more Guerbet alcohols with a pour point below 6°C which correspond to general formula (I):
R¹-CH (CH₂OH) -R (I)
in which R¹ and R independently of one another represent an alkyl group containing 6 to 12 carbon atoms, with the proviso that the total number of carbon atoms per alcohol molecule is in the range from 16 to 24,
are used in the oiling of leather. - The use claimed in claim 1, characterized in that the Guerbet alcohols have a pour point below -10°C.
- The use claimed in claim 1 or 2, characterized in that 2-hexyldecan-1-ol and/or 2-octyldodecan-1-ol is/are used as the Guerbet alcohols.
- Fatty spew inhibiting compositions containing an oiling component and a fatty spew inhibiting additive, characterized in that the additive comprises one or more Guerbet alcohols with a pour point below 6°C which correspond to general formula (I):
R¹-CH(CH₂OH)-R (I)
in which R¹ and R independently of one another represent an alkyl group containing 6 to 12 carbon atoms, with the proviso that the total number of carbon atoms per alcohol molecule is in the range from 16 to 24. - A composition as claimed in claim 4, characterized in that the oiling component is a neutral fat.
- A process for oiling leather in which tanned leather is treated with an oiling component and a fatty spew inhibiting additive, characterized in that one or more Guerbet alcohols with a pour point below 6°C which correspond to general formula (I):
R¹-CH(CH₂OH)-R (I)
in which R¹ and R independently of one another represent an alkyl group containing 6 to 12 carbon atoms, with the proviso that the total number of carbon atoms per alcohol molecule is in the range from 16 to 24,
is/are used as the additive. - A process as claimed in claim 6, characterized in that a neutral fat is predominantly used as the oiling component.
- A process as claimed in claim 6 or 7, characterized in that chrome-tanned leather is used.
- A process as claimed in any of claims 6 to 8, characterized in that the Guerbet alcohols have a pour point below -10°C.
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DE4223706A DE4223706A1 (en) | 1992-07-18 | 1992-07-18 | Use of Guerbet alcohols to prevent fat rash on leather |
DE4223706 | 1992-07-18 | ||
PCT/EP1993/001806 WO1994002651A1 (en) | 1992-07-18 | 1993-07-10 | Use of guerbet alcohols to prevent the formation of fatty spew on leather |
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EP (1) | EP0651828B1 (en) |
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DE4405415A1 (en) * | 1994-02-21 | 1995-08-24 | Henkel Kgaa | Use of sulfated substances to grease leather |
US6630001B2 (en) | 1998-06-24 | 2003-10-07 | International Heart Institute Of Montana Foundation | Compliant dehyrated tissue for implantation and process of making the same |
US6352708B1 (en) | 1999-10-14 | 2002-03-05 | The International Heart Institute Of Montana Foundation | Solution and method for treating autologous tissue for implant operation |
KR101883189B1 (en) * | 2016-07-19 | 2018-07-31 | 주식회사 대호레더 | Manufacturing method of natural leather with prevented whitening phenomenon |
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FR2136961A1 (en) * | 1971-05-10 | 1972-12-29 | Vichemont Marcel | Leather conditioning compsn - for improved permeability water vapour |
AR202669A1 (en) * | 1973-11-03 | 1975-06-30 | Henkel & Cie Gmbh | COMPOSITION FOR THE PREPARATION OF LEATHERS RESISTANT TO THE ACTION OF WATER AND THE CORRESPONDING PROCEDURE |
US4299994A (en) * | 1980-02-06 | 1981-11-10 | Sandoz, Inc. | Polyoxyalkylene condensation products |
WO1990015127A1 (en) * | 1989-06-09 | 1990-12-13 | Ag-Seed Pty Limited | Artificial jojoba oil |
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