EP0849365B1 - Preparation agent for leather - Google Patents
Preparation agent for leather Download PDFInfo
- Publication number
- EP0849365B1 EP0849365B1 EP97810974A EP97810974A EP0849365B1 EP 0849365 B1 EP0849365 B1 EP 0849365B1 EP 97810974 A EP97810974 A EP 97810974A EP 97810974 A EP97810974 A EP 97810974A EP 0849365 B1 EP0849365 B1 EP 0849365B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- agent
- composition according
- weight
- retanning
- fatliquoring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
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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
- C14C3/00—Tanning; Compositions for tanning
-
- 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 present invention relates to new agents for simultaneous retanning and oiling of pre-tanned leather or furs, processes for making these agents and the Use of these agents for the production of leather or furs.
- the pre-tanned hides are usually neutralized, then retanned, greased and, if necessary, subsequently colored and even further equipped.
- the operations that start with neutralization are often in separate baths or carried out in succession in a bath, but can also in a bath take place at the same time.
- the products used are usually individually in solid or liquid form used because it is difficult to mix homogeneous manufacture.
- the fatliquors are almost exclusively liquid or at least wax-like and can be mixed with the solid components, e.g. the neutralizing agents and retanning agents, do not process into mixtures according to previously known methods, in which for a sufficiently long time and also at different temperatures a homogeneous distribution of the components and sufficient storage stability are guaranteed.
- the agents according to the invention when used, synergistic effect. You can namely the amount of retanning and Significantly reduce fatliquoring compared to a method in which this Chemicals are used individually, although the usual retanning and greasing agents be used. In particular, the fat emulsification when using the Improved agents according to the invention and one arrives with smaller amounts Fatty substances.
- the agents according to the invention are excellent Storage stability and are frost-resistant, if it is solid agents.
- the transport and Storage effort compared to the use of special funds for each individual Treatment step can be significantly reduced and handling becomes significant simplified. They also save up to 60% water and time facilitate the reproducibility of the quality of the leather obtained. Furthermore, through the use of the agents according to the invention the penetration and distribution of the Chemicals in the leather are accelerated and / or improved. This leads e.g. to a better coloring of the leather. In addition, other important properties of the Leather, such as behavior towards water, fogging behavior, adhesive strength of dressing films, stretch and strength properties as well as the mass per unit area beneficially influenced.
- the agents according to the invention are preferably in such a form that they are usual stirring in water from 10 to 60 ° C are homogeneously distributable to form Suspensions or dispersions that are stable for the duration of the leather treatment.
- usual stirring in here is simple stirring using in Leather stirrers used to understand.
- the agents according to the invention are preferably in such a form that they the addition to water form micelles containing retanning agents and fatliquoring agents.
- the particles preferably 50% of the particles have one. Size under 15 ⁇ m.
- agents according to the invention which are particularly preferred are: the addition to water form micelles in which 90% of the particles have a size below 40 ⁇ m.
- the agents according to the invention are suitable for the treatment of for wet dressing prepared so-called semi-finished product, i.e. pre-tanned leather, e.g. Wetblue and Wetwhite.
- the retanning agents can be of natural or synthetic origin. In consideration for example, come the connections commonly used today, for example vegetable tannins, aromatic syntans, resin tannins, Reactive tanning agents, mineral and polymeric tanning agents.
- Suitable vegetable tannins are e.g. Tannins made from mimosa, quebracho, oak, Chestnut or spruce bark can be obtained. Vegetable are particularly suitable Tannins that contain pyrogallol or pyrocatechin (pyrocatechol).
- Aromatic syntane e.g. consider such connections through Condensation of sulfonated aromatic compounds alone or together with further, mostly unsulfonated aromatic compounds with formaldehyde and / or Urea are available.
- Aromatic compounds suitable for this are, for example: naphthalene, diphenyl, terphenyl, Phenols, cresols, 4,4'-dihydroxidiphenyl sulfone, ⁇ -naphthol, dihydroxybenzenes, resorcinol, 2,2'-bis (hydroxyphenyl) propane and diaryl ethers such as diphenyl ether and ditolyl ether which optionally sulfonated in a manner known per se.
- condensation products are in the form of the free acids, preferably in the form of the Sulfonic acids, or as salts, especially ammonium, lithium, potassium or in particular Sodium salts.
- condensation products are known, for example from Ullmann's Encyclopedia of Industrial Chemistry Vol. 16, (4), 138 to 140 (1979) or can be prepared by the processes described in the references given there.
- Resin tanning agents e.g. the cationic condensation products containing nitrogen organic compounds, e.g. Urea, thiourea, dicyandiamide or melamine, with formaldehyde or other simple oxo compounds.
- nitrogen organic compounds e.g. Urea, thiourea, dicyandiamide or melamine
- Suitable resin tanning agents are the anionic compounds that are obtained if one condenses products of nitrogenous organic compounds, e.g. Urea, thiourea, dicyandiamide or melamine, with formaldehyde or others simple oxo compounds and anionic compounds such as e.g. phenols, Alkali salts of aromatic sulfonic acids, sulfonamides, lignin sulfonates, sulfite or Hydrogen sulfite condenses.
- nitrogenous organic compounds e.g. Urea, thiourea, dicyandiamide or melamine
- formaldehyde or others simple oxo compounds such as e.g. phenols, Alkali salts of aromatic sulfonic acids, sulfonamides, lignin sulfonates, sulfite or Hydrogen sulfite condenses.
- Particularly preferred resin tanning agents are the condensation products of urea Formaldehyde and dicyandiamide-based resin tanning agents.
- Suitable reactive tanning agents are e.g. Mono-, di- and polyaldehydes, in particular Glutaraldehyde, multifunctional isocyanates, alkyl sulfochlorides, higher molecular weight Alkyl sulfonates and monomeric vinyl and acrylic derivatives and their polymers.
- chromium, aluminum, iron or come as mineral retanning agents Zirconium salts for example chromium (III) chloride or sulfate, chromium alum, optionally basic aluminum chloride or sulfate, iron (III) chloride or sulfate, Zirconium oxychloride and zirconium sulfate.
- the polymeric retanning agents are e.g. polyacrylates, copolymers, containing acrylates, polyurethanes or polybutadienes.
- Vegetable tanning agents are preferably used as tanning agents in the agents according to the invention, aromatic syntans or reactive tanning agents used.
- These fatliquoring agents are preferably by sulfation, sulfitation or formation of Modified sulfonic acids so that they are soluble or emulsifiable in water.
- lubricants are preferably used as aqueous solutions or emulsions used.
- the agents for producing leather according to the invention can each have a single agent Contain neutralizers, a retanning agent and a fatliquor, but they can also contain mixtures of two and more of these components. This is even normally the case because these connections are rarely Pure substances, but technical mixtures of numerous, more or less similar connections.
- Leather treatment agents contain further additives, e.g. Neutralizing agents, carriers, Dyes, impregnating agents, dressing agents and dressing aids.
- Suitable neutralizing agents for the inventive Agents are, for example, alkali salts of weak inorganic or organic Acids, aromatic sulfonic acids or aliphatic mono- or dicarboxylic acids. It is preferably sodium or potassium bicarbonate, formate or acetate, around oxalic acid, malonic acid, adipic acid or condensed sulfonated phenols. Sodium bicarbonate, sodium formate, acetic acid, adipic acid or are particularly suitable sulfonated diphenyl sulfones.
- Suitable carriers are e.g. Sodium chloride, Glauber's salt, sodium formate, protein powder, Starch, kaolin, polysaccharides, glucose or gelatin.
- Suitable dyes are the leather dyes usually used, for example natural dyes, also synthetic dyes, such as e.g. anionic Dyes, metal complex dyes, direct dyes, cationic dyes or Sulfur dyes. Pigments are also included among dyes, i.e. largely in water to understand insoluble dyes.
- the impregnating agents are also those in the leather industry known means used, e.g. to means of protection against water, organic Solvents or oils or against dirt, means to improve the Resistance to abrasion, abrasion or other mechanical injuries, Means for improving the temperature resistance or light fastness and Flammability reduction or anti-static.
- Suitable dressing agents are e.g. Primers such as polyacrylates, butadiene copolymers or polyurethanes, or finishing agents, such as casein, nitrocellulose or Polyurethane formulations.
- preparation aids come the well-known and used in practice into question, for example penetrators, primers and fillers, anti-adhesive agents, Thickening and stabilizing agents, plasticizers, matting agents, grip agents and Fixative.
- agents according to the invention are also possible in the form of solutions, dispersions or emulsions in a suitable solvent, preferably in water, use.
- the percentages relate to the total weight of the funds Leather treatment.
- the agents according to the invention are produced in a manner known per se and Way, for example by adding a retanning agent, a fatliquor and if necessary, other additives are mixed undiluted.
- a retanning agent and fatliquor and any further ones that may be present Select additives so that the agents obtained when added to the minimum 8 times the amount of water at 10 to 60 ° C give homogeneous mixtures.
- retanning agents are preferably used Additions as solutions or suspensions or dispersions, mixes them and then dries.
- water preferably serves as Solvents, but there are also organic solvents, for example one or polyhydric alcohols or hydrocarbons.
- Drying is done in the usual way, but should normally be done under conditions be carried out in which the homogeneous distribution of the constituents of the mixtures preserved. If all components are readily soluble in water or easily emulsifiable or are dispersible, the type of drying does not matter.
- It is preferably dried by spray drying at about 80 to 140 ° C, especially at 100 to 120 ° C.
- a first Carrier material for example sodium chloride, Glauber's salt, sodium formate, protein powder or starch to spray and dry at the same time or subsequently.
- the agents according to the invention are obtained in the form of powder or Granules in this form for the preparation of aqueous liquors for leather production can be used.
- the funds are not dusting, can be easily homogenized in Distribute water and remain free-flowing even after long storage, even with Temperatures up to approx. 40 ° C. If you don't have a carrier material or as such a non-salt one Used compound, the agents according to the invention can be salt-free or produce low in salt, which during further processing, e.g. with simultaneous or subsequent dyeing is often advantageous and relieves the environment.
- the agents according to the invention are suitable for producing various types of leather, for example for full-grain, slightly or heavily retanned leather or suede from Goat, sheep, beef or pork. With these means, leather is for everyone Usable uses, such as shoe, furniture, car, clothing and Bag leather.
- the agents according to the invention are also suitable for retanning and oiling of fur, whereby the hair is largely unaffected.
- the leather can be produced in all machines customary for wet finishing be carried out, for example barrel, Dosamat, tanning machine or mixer.
- the production takes place e.g. by using pre-tanned leather such as Wetblue or Wetwhite at 10 - 50 ° C in 50 - 300% water, based on the weight of the substrate, presents, then adds 5 - 30% of the agent according to the invention and this during 30 - Allows to act for 180 minutes at the stated temperature with circulation. Subsequently if necessary, 1-3% formic acid is added in two parts over 15 minutes and continue treatment for 40-60 minutes. Then let the fleet run off, rinses with 100 - 300% water for 5 - 10 minutes, drains the washing solution and completes in the usual way.
- pre-tanned leather such as Wetblue or Wetwhite at 10 - 50 ° C in 50 - 300% water, based on the weight of the substrate, presents, then adds 5 - 30% of the agent according to the invention and this during 30 - Allows to act for 180 minutes at the stated temperature with circulation. Subsequently if necessary, 1-3% formic acid is added in two parts over
- Example 1 The following components are mixed at room temperature to form a homogeneous mixture:
- a neutralizing agent approximately 12.5 Parts of a neutralizing agent (approx. 35% aqueous solution of a mixture of aromatic sulfonic acids with aliphatic dicarboxylic acids), 12.5 Parts of a penetration aid (approx. 50% aqueous solution of a condensation product of aromatic sulfonic acids), 10.0 Parts of a retanning agent (approx. 50% aqueous solution of a mixture of a vegetable tanning agent and a tanning condensation product of aromatic sulfones), 15.0 Parts of a retanning agent (approx. 55% aqueous solution of a condensation product of phenolsulfonic acid and aromatic hydroxysulfones), 47.5 Parts of a fatliquor (approx. 50% aqueous solution of a fatliquor based on sulfited natural and synthetic fats) and 2.5 Parts of a stabilizer for the fatliquor (sulfated fatty alcohol).
- This mixture is spray dried at normal pressure and 110 ° C. You get a powder which is suitable for wet dressing wetblue and wetwhite, especially for Manufacture of furniture and car upholstery leather and shoe leather.
- Example 2 The following components are mixed at room temperature to form a homogeneous mixture:
- a neutralizing agent approximately 12.5 Parts of a neutralizing agent (approx. 35% aqueous solution of a mixture of aromatic sulfonic acids with aliphatic dicarboxylic acids), 12.5 Parts of a penetration aid (approx. 50% aqueous solution of a condensation product of aromatic sulfonic acids), 10.0 Parts of a retanning agent (approx. 30% aqueous solution of an acrylate copolymer), 15.0 Parts of a retanning agent (approx. 55% aqueous solution of a condensation product of aromatic hydroxysulfones and sulfonic acids), 47.5 Parts of a fatliquor (approx. 50% aqueous solution of a fatliquor based on sulfited natural and synthetic fats) and 2.5 Parts of a stabilizer for the fatliquor (sulfated fatty alcohol).
- This mixture is spray dried at normal pressure and 110 ° C. You get a powder which is suitable for wet dressing wetblue and wetwhite, especially for Manufacture of furniture and car upholstery leather and shoe leather.
- Example 3 The following components are mixed at room temperature to form a homogeneous mixture:
- a retanning agent approximately 50% aqueous solution of a condensation product of sulfones and sulfonic acids of cyclic compounds
- 20.0 Parts of a retanning agent approximately 50% aqueous solution of a mixture of a vegetable tanning agent and a tanning condensation product of aromatic sulfones
- 20.0 Parts of a liquid melamine resin 12.0 Parts of a retanning agent (approx. 30% aqueous solution of an acrylate copolymer)
- a fatliquor approximatelyx. 50% aqueous solution of a fatliquor based on sulfited natural and synthetic fats.
- This mixture is spray dried at normal pressure and 110 ° C. You get a powder which is suitable for wet dressing wetblue and wetwhite, especially for Manufacture of upper leather.
- the leather obtained is significantly softer than leather produced in a conventional manner, the neutralization, retanning and oiling in each case individually be carried out one after the other. It also has better tear resistance and lower fogging values at lower manufacturing costs.
- Example 5 The following components are mixed at room temperature to form a homogeneous mixture:
- a neutralizing agent approximately 35% aqueous solution of a mixture of aromatic sulfonic acids with aliphatic dicarboxylic acids
- a penetration aid approximately 50% aqueous solution of a condensation product of aromatic sulfonic acids
- 10.0 Parts of a retanning agent approximately 50% aqueous solution of a mixture of a vegetable tanning agent and a tanning condensation product of aromatic sulfones
- 15.0 Parts of a retanning agent approximately 47.5 Parts of a fatliquor (approx.
- aqueous solution of a fatliquor based on sulfited natural and synthetic fats 50% aqueous solution of a fatliquor based on sulfited natural and synthetic fats), 2.5 Parts of a stabilizer for the fatliquor (sulfated fatty alcohol), 32.0 Portions of an aqueous dye formulation containing 40% by weight of the black dye C.I. Acid Black 210 and 4.0 Parts of an aqueous dye formulation containing about 50% by weight of carbon black.
- This mixture is spray dried at normal pressure and 110 ° C.
- Example 4 Works as described in example 4, but uses instead of the agent according to Example 1 20% of the mixture described above, so no matter black dyed leather, which shows a significantly better coloring than on conventional Leather made wisely, in the manufacture of which neutralization, retanning, Greasing and coloring are carried out one after the other.
- Example 6 The following components are mixed at room temperature to form a homogeneous mixture:
- a vegetable tannin 15.0 Parts of a retanning agent (approx. 50% aqueous solution of a tanning condensation product of aromatic sulfones), 5.5 Parts of a retanning agent (approx. 40% aqueous solution of an acrylate copolymer), 26.5 Parts of a neutralizing agent (approx. 50% aqueous solution of a mixture of aromatic sulfonic acids with aliphatic dicarboxylic acids), 5.5 Parts of a penetration aid (approx. 40% aqueous solution of a condensation product of aromatic sulfonic acids), 30.5 Parts of a fatliquor (approx. 50% aqueous solution of a fatliquor based on sulfited natural and synthetic fats), 13.0 Parts of a carrier (Glauber's salt).
- a retanning agent approximately 50% aqueous solution of a tanning condensation product of aromatic sulfones
- This mixture is spray dried at normal pressure and 110 ° C. You get a powder which is suitable for wet dressing of wetblue and wet white, especially for Manufacture of upper leather.
- a piece of Wetblue (beef) 1.9 mm folded in a barrel in 30% water at 30 ° is added, and 15% of the agent according to Example 6 is added and treated at 30 ° for 30 minutes. Then add 3% of the black powder dye CIAcid Black 210 and treat for 90 minutes at 30 °.
- the leather obtained is significantly softer than leather produced in a conventional manner, the neutralization, retanning and oiling in each case individually be carried out one after the other.
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Medicinal Preparation (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Die vorliegende Erfindung betrifft neue Mittel zur gleichzeitigen Nachgerbung und Fettung von vorgegerbtem Leder oder Pelzen, Verfahren zur Herstellung dieser Mittel sowie die Verwendung dieser Mittel zur Herstellung von Leder oder Pelzen.The present invention relates to new agents for simultaneous retanning and oiling of pre-tanned leather or furs, processes for making these agents and the Use of these agents for the production of leather or furs.
Bei der Herstellung von Leder werden üblicherweise die vorgegerbten Häute neutralisiert, dann nachgegerbt, gefettet und gegebenenfalls anschliessend gefärbt und noch weiter ausgerüstet. Die mit der Neutralisation beginnenden Arbeitsgänge werden häufig in getrennten Bädem oder nacheinander in einem Bad durchgeführt, können aber auch in einem Bad gleichzeitig stattfinden. Die dabei eingesetzten Produkte werden meist einzeln in fester oder flüssiger Form verwendet, da es schwierig ist, homogene Mischungen herzustellen. Die Fettungsmittel sind nämlich fast ausschliesslich flüssig oder zumindest wachsartig und lassen sich mit den festen Komponenten, z.B. den Neutralisationsmitteln und Nachgerbstoffen, nach bisher bekannten Methoden nicht zu Mischungen verarbeiten, bei denen während ausreichend langer Zeit und auch bei unterschiedlichen Temperaturen eine homogene Verteilung der Komponenten und eine genügende Lagerstabilität gewährleistet sind.In the production of leather, the pre-tanned hides are usually neutralized, then retanned, greased and, if necessary, subsequently colored and even further equipped. The operations that start with neutralization are often in separate baths or carried out in succession in a bath, but can also in a bath take place at the same time. The products used are usually individually in solid or liquid form used because it is difficult to mix homogeneous manufacture. The fatliquors are almost exclusively liquid or at least wax-like and can be mixed with the solid components, e.g. the neutralizing agents and retanning agents, do not process into mixtures according to previously known methods, in which for a sufficiently long time and also at different temperatures a homogeneous distribution of the components and sufficient storage stability are guaranteed.
Es wurden nun neue Präparate gefunden, die eine bedeutende Vereinfachung der Nasszurichtung von Leder ermöglichen, da mit nur einem Mittel gleichzeitig das Nachgerben und das Fetten sowie eventuell noch weitere Behandlungen durchgeführt werden können. Dies ist dadurch bedingt, dass in diesen Mitteln Nachgerbmittel und Fettungsmittel in solcher Form vorliegen, dass sie bei der Zugabe zu der mindestens 8fachen Menge Wasser bei 10 bis 60 °C homogene Mischungen ergeben.New preparations have now been found which significantly simplify the process Allow wet dressing of leather, because with only one agent at the same time Retanning and greasing as well as possibly other treatments carried out can be. This is due to the fact that in these funds retanning agents and Fatting agents are present in such a form that they are added to the minimum 8 times the amount of water at 10 to 60 ° C give homogeneous mixtures.
Überraschenderweise tritt bei Verwendung der erfindungsgemässen Mittel,ein synergistischer Effekt auf. Man kann nämlich die Einsatzmenge an Nachgerb- und Fettungsmittel deutlich vermindern, gegenüber einer Arbeitsweise, bei der diese Chemikalien einzeln eingesetzt werden, obwohl die üblichen Nachgerb- und Fettungsmittel verwendet werden. Insbesondere ist die Fettemulgierung bei Verwendung der erfindungsgemässen Mittel verbessert und man kommt mit geringeren Mengen an Fettungsmitteln aus. Die erfindungsgemässen Mittel weisen eine hervorragende Lagerstabilität auf und sind frostfest, falls es sich um feste Mittel handelt.Surprisingly, when the agents according to the invention are used, synergistic effect. You can namely the amount of retanning and Significantly reduce fatliquoring compared to a method in which this Chemicals are used individually, although the usual retanning and greasing agents be used. In particular, the fat emulsification when using the Improved agents according to the invention and one arrives with smaller amounts Fatty substances. The agents according to the invention are excellent Storage stability and are frost-resistant, if it is solid agents.
Bei Verwendung der erfindungsgemässen Mittel kann ausserdem der Transport- und Lageraufwand gegenüber der Verwendung spezieller Mittel für jeden einzelnen Behandlungsschritt deutlich reduziert werden und die Handhabung wird erheblich vereinfacht. Zudem bringen sie eine Wasser- und Zeitersparnis von bis zu 60 % und erleichtern die Reproduzierbarkeit der Qualität des erhaltenen Leders. Darüberhinaus wird durch die Verwendung der erfindungsgemässen Mittel die Penetration und Verteilung der Chemikalien in das Leder beschleunigt und/oder verbessert. Dies führt z.B. zu einer besseren Durchfärbung des Leders. Ausserdem werden weitere wichtige Eigenschaften des Leders, wie das Verhalten gegenüber Wassereinwirkung, Foggingverhalten, Haftfestigkeit von Zurichtfilmen, Dehnungs- und Festigkeitseigenschaften sowie die Flächenmasse vorteilhaft beeinflusst.When using the means according to the invention, the transport and Storage effort compared to the use of special funds for each individual Treatment step can be significantly reduced and handling becomes significant simplified. They also save up to 60% water and time facilitate the reproducibility of the quality of the leather obtained. Furthermore, through the use of the agents according to the invention the penetration and distribution of the Chemicals in the leather are accelerated and / or improved. This leads e.g. to a better coloring of the leather. In addition, other important properties of the Leather, such as behavior towards water, fogging behavior, adhesive strength of dressing films, stretch and strength properties as well as the mass per unit area beneficially influenced.
Gegenstand der vorliegenden Erfindung sind somit Mittel zur Herstellung von Leder oder
Pelzen, dadurch gekennzeichnet, dass sie, bezogen auf das Gesamtgewicht des Mittels,
Die erfindungsgemässen Mitteln liegen vorzugsweise in solcher Form vor, dass sie durch übliches Einrühren in Wasser von 10 bis 60 °C homogen verteilbar sind unter Bildung von Suspensionen oder Dispersionen, die während der Dauer der Lederbehandlung stabil sind. Unter üblichem Einrühren ist hier einfaches Rühren unter Verwendung von in der Lederindustrie verwendeten Rührern zu verstehen.The agents according to the invention are preferably in such a form that they are usual stirring in water from 10 to 60 ° C are homogeneously distributable to form Suspensions or dispersions that are stable for the duration of the leather treatment. With usual stirring in here is simple stirring using in Leather stirrers used to understand.
Die erfindungsgemässen Mittel liegen vorzugsweise in einer solchen Form vor, dass sie bei der Zugabe zu Wasser Micellen bilden, enthaltend Nachgerbmittel und Fettungsmittel.The agents according to the invention are preferably in such a form that they the addition to water form micelles containing retanning agents and fatliquoring agents.
In den Dispersionen oder Suspensionen besitzt vorzugsweise 50 % der Teilchen eine. Grösse unter 15µm. Besonders bevorzugt sind solche erfindungsgemässen Mittel, die bei der Zugabe zu Wasser Micellen bilden, bei denen 90 % der Teilchen eine Grösse unter 40 µm besitzen.In the dispersions or suspensions, preferably 50% of the particles have one. Size under 15µm. Those agents according to the invention which are particularly preferred are: the addition to water form micelles in which 90% of the particles have a size below 40 µm.
Die erfindungsgemässen Mittel eignen sich für die Behandlung von für die Nasszurichtung vorbereitetem sog. Halbfabrikat, d.h. vorgegerbtem Leder, z.B. Wetblue und Wetwhite.The agents according to the invention are suitable for the treatment of for wet dressing prepared so-called semi-finished product, i.e. pre-tanned leather, e.g. Wetblue and Wetwhite.
Die Nachgerbstoffe können natürlicher oder synthetischer Herkunft sein. In Betracht kommen zum Beispiel die heutzutage üblicherweise verwendeten Verbindungen, beispielsweise pflanzliche Gerbstoffe, aromatische Syntane, Harzgerbstoffe, Reaktivgerbstoffe, mineralische und polymere Gerbstoffe.The retanning agents can be of natural or synthetic origin. In consideration for example, come the connections commonly used today, for example vegetable tannins, aromatic syntans, resin tannins, Reactive tanning agents, mineral and polymeric tanning agents.
Geeignete pflanzliche Gerbstoffe sind z.B. Gerbstoffe, die aus Mimosa, Quebracho, Eiche, Kastanie oder Fichtenrinde gewonnen werden. Besonders geeignet sind pflanzliche Gerbstoffe, die Pyrogallol oder Pyrocatechin (Brenzcatechin) enthalten.Suitable vegetable tannins are e.g. Tannins made from mimosa, quebracho, oak, Chestnut or spruce bark can be obtained. Vegetable are particularly suitable Tannins that contain pyrogallol or pyrocatechin (pyrocatechol).
Als aromatische Syntane kommen z.B. solche Verbindungen in Betracht, welche durch Kondensation von sulfonierten aromatischen Verbindungen allein oder zusammen mit weiteren, meist unsulfonierten aromatischen Verbindungen mit Formaldehyd und/oder Harnstoff erhältlich sind.Aromatic syntane e.g. consider such connections through Condensation of sulfonated aromatic compounds alone or together with further, mostly unsulfonated aromatic compounds with formaldehyde and / or Urea are available.
Hierfür geeignete aromatische Verbindungen sind z.B.: Naphthalin, Diphenyl, Terphenyl, Phenole, Kresole, 4,4'-Dihydroxidiphenylsulfon, β-Naphthol, Dihydroxibenzole, Resorcin, 2,2'-Bis(hydroxyphenyl)propan und Diarylether, wie Diphenylether und Ditolylether, die gegebenenfalls in an sich bekannter Weise sulfoniert wurden.Aromatic compounds suitable for this are, for example: naphthalene, diphenyl, terphenyl, Phenols, cresols, 4,4'-dihydroxidiphenyl sulfone, β-naphthol, dihydroxybenzenes, resorcinol, 2,2'-bis (hydroxyphenyl) propane and diaryl ethers such as diphenyl ether and ditolyl ether which optionally sulfonated in a manner known per se.
Besonders geeignete anionische aromatische Synthane sind die folgenden Verbindungen:
Diese Kondensationsprodukte liegen in Form der freien Säuren, vorzugsweise in Form der Sulfonsäuren, oder als Salze, vor allem Ammonium-, Lithium-, Kalium- oder insbesondere Natriumsalze vor.These condensation products are in the form of the free acids, preferably in the form of the Sulfonic acids, or as salts, especially ammonium, lithium, potassium or in particular Sodium salts.
Diese Kondensationsprodukte sind bekannt, z.B. aus Ullmanns Enzyklopädie der technischen Chemie Bd. 16, (4), 138 bis 140 (1979) oder können nach den in den dort angegebenen Referenzen beschriebenen Verfahren hergestellt werden.These condensation products are known, for example from Ullmann's Encyclopedia of Industrial Chemistry Vol. 16, (4), 138 to 140 (1979) or can be prepared by the processes described in the references given there.
Als Harzgerbstoffe kommen z.B. die kationische Kondensationsprodukte stickstoffhaltiger organischer Verbindungen, wie z.B. Hamstoff, Thioharnstoff, Dicyandiamid oder Melamin, mit Formaldehyd oder anderen einfachen Oxo-Verbindungen in Betracht. Resin tanning agents e.g. the cationic condensation products containing nitrogen organic compounds, e.g. Urea, thiourea, dicyandiamide or melamine, with formaldehyde or other simple oxo compounds.
Weitere geeignete Harzgerbstoffe sind die anionischen Verbindungen, die man erhält, wenn man Kondensationsprodukte stickstoffhaltiger organischer Verbindungen, wie z.B. Hamstoff, Thiohamstoff, Dicyandiamid oder Melamin, mit Formaldehyd oder anderen einfachen Oxo-Verbindungen und anionischen Verbindungen, wie z.B. Phenolen, Alkalisalzen aromatischer Sulfonsäuren, Sulfonamiden, Ligninsulfonaten, Sulfit oder Hydrogensulfit kondensiert.Other suitable resin tanning agents are the anionic compounds that are obtained if one condenses products of nitrogenous organic compounds, e.g. Urea, thiourea, dicyandiamide or melamine, with formaldehyde or others simple oxo compounds and anionic compounds such as e.g. phenols, Alkali salts of aromatic sulfonic acids, sulfonamides, lignin sulfonates, sulfite or Hydrogen sulfite condenses.
Besonders bevorzugte Harzgerbstoffe sind die Kondensationsprodukte von Harnstoff mit Formaldehyd und Harzgerbstoffe auf Dicyandiamid-Basis.Particularly preferred resin tanning agents are the condensation products of urea Formaldehyde and dicyandiamide-based resin tanning agents.
Geeignete Reaktivgerbstoffe sind z.B. Mono-, Di- und Polyaldehyde, insbesondere Glutaraldehyd, mehrfunktionelle isocyanate, Alkylsulfochloride, höhermolekulare Alkylsulfonate sowie monomere Vinyl- und Acrylderivate und deren Polymerisate.Suitable reactive tanning agents are e.g. Mono-, di- and polyaldehydes, in particular Glutaraldehyde, multifunctional isocyanates, alkyl sulfochlorides, higher molecular weight Alkyl sulfonates and monomeric vinyl and acrylic derivatives and their polymers.
Als mineralische Nachgerbstoffe kommen die bekannten Chrom-, Aluminium-, Eisen- oder Zirkoniumsalze in Betracht, beispielsweise Chrom(III)-chlorid oder - sulfat, Chromalaun, gegebenenfalls basisches Aluminiumchlorid oder -sulfat, Eisen(lll)-chlorid oder -sulfat, Zirkonoxychlorid und Zirkoniumsulfat.The well-known chromium, aluminum, iron or come as mineral retanning agents Zirconium salts, for example chromium (III) chloride or sulfate, chromium alum, optionally basic aluminum chloride or sulfate, iron (III) chloride or sulfate, Zirconium oxychloride and zirconium sulfate.
Bei den polymeren Nachgerbstoffen handelt es sich z.B. um Polyacrylate, Copolymere, enthaltend Acrylate, Polyurethane oder Polybutadiene.The polymeric retanning agents are e.g. polyacrylates, copolymers, containing acrylates, polyurethanes or polybutadienes.
Diese Nachgerbstoffe sind bekannt und zum grossen Teil im Handel erhältlich.These retanning agents are known and a large part of them are commercially available.
In den erfindungsgemässen Mitteln werden als Gerbstoffe bevorzugt pflanzliche Gerbstoffe, aromatische Syntane oder Reaktivgerbstoffe eingesetzt.Vegetable tanning agents are preferably used as tanning agents in the agents according to the invention, aromatic syntans or reactive tanning agents used.
Als Fettungsmittel kommen die üblichen für die Fettung von Leder gebräuchlichen Mittel in
Betracht. Es handelt sich vorzugsweise um
Vorzugsweise sind diese Fettungsmittel durch Sulfatierung, Sulfitierung oder Bildung von Sulfonsäuren modifiziert, so dass sie in Wasser löslich oder emulgierbar sind. Man kann auch ein Fettungsmittelgemisch einsetzen, dessen einer Teil emulgierende Eigenschaften besitzt und so für den restlichen Teil als Emulgator wirkt. Geeignet sind hierfür z. B. sulfatierte Fettalkohole.These fatliquoring agents are preferably by sulfation, sulfitation or formation of Modified sulfonic acids so that they are soluble or emulsifiable in water. One can also use a fat mixture, some of which has emulsifying properties possesses and thus acts as an emulsifier for the remaining part. Suitable for this are, for. B. sulfated fatty alcohols.
Diese Fettungsmittel werden vorzugsweise als wässrige Lösungen oder Emulsionen eingesetzt.These lubricants are preferably used as aqueous solutions or emulsions used.
Die erfindungsgemässen Mittel zur Herstellung von Leder können jeweils ein einziges Neutralisationsmittel, ein Nachgerbmittel und ein Fettungsmittel enthalten, sie können aber auch Mischungen aus jeweils zwei und mehreren dieser Komponenten enthalten. Dies ist sogar normalerweise der Fall, da es sich bei diesen Verbindungen nur selten um Reinsubstanzen, sondem um technische Mischungen aus zahlreichen, mehr oder weniger ähnlichen Verbindungen handelt.The agents for producing leather according to the invention can each have a single agent Contain neutralizers, a retanning agent and a fatliquor, but they can also contain mixtures of two and more of these components. This is even normally the case because these connections are rarely Pure substances, but technical mixtures of numerous, more or less similar connections.
Neben Nachgerbmittel und Fettungsmittel können die erfindungsgemässen Lederbehandlungsmittel weitere Zusätze enthalten, z.B. Neutralisationsmittel, Trägerstoffe, Farbstoffe, Imprägniermittel, Zurichtmittel und Zuricht-Hilfsmittel.In addition to retanning agents and fatliquoring agents, those according to the invention can be used Leather treatment agents contain further additives, e.g. Neutralizing agents, carriers, Dyes, impregnating agents, dressing agents and dressing aids.
Als Neutralisationsmittel kommen die bekannten Verbindungen in Betracht, mit denen die stark sauren vorgegerbten Leder in schonender Weise neutralisiert werden können. Unter Neutralisationsmittel sind auch solche Verbindungen zu verstehen, die den pH-Wert der stark sauren vorgegerbten Leder erhöhen, z.B. auf 4,5, ohne dass der neutrale pH-Wert von 7 erreicht werden kann. Geeignete Neutralisationsmittel für die erfindungsgemässen Mittel sind beispielsweise Alkalisalze von anorganischen oder organischen schwachen Säuren, aromatische Sulfonsäuren oder aliphatische Mono- oder Dicarbonsäuren. Vorzugsweise handelt es sich um Natrium- oder Kalium-bicarbonat, -formiat, oder -acetat, um Oxalsäure, Malonsäure, Adipinsäure oder um kondensierte sulfonierte Phenole. Besonders geeignet sind Natriumbicarbonat, Natriumformiat, Essigsäure, Adipinsäure oder sulfonierte Diphenylsulfone.The known compounds with which the strongly acidic pretanned leather can be neutralized in a gentle way. Under Neutralizing agents are also to be understood as those compounds which control the pH of the increase strongly acidic pretanned leather, e.g. to 4.5 without the neutral pH of 7 can be achieved. Suitable neutralizing agents for the inventive Agents are, for example, alkali salts of weak inorganic or organic Acids, aromatic sulfonic acids or aliphatic mono- or dicarboxylic acids. It is preferably sodium or potassium bicarbonate, formate or acetate, around oxalic acid, malonic acid, adipic acid or condensed sulfonated phenols. Sodium bicarbonate, sodium formate, acetic acid, adipic acid or are particularly suitable sulfonated diphenyl sulfones.
Geeignete Trägerstoffe sind z.B. Natriumchlorid, Glaubersalz, Natriumformiat, Proteinpulver, Stärke, Kaolin, Polysaccharide, Glucose oder Gelatine.Suitable carriers are e.g. Sodium chloride, Glauber's salt, sodium formate, protein powder, Starch, kaolin, polysaccharides, glucose or gelatin.
Als Farbstoffe kommen die üblicherweise eingesetzten Lederfarbstoffe in Frage, beispielsweise natürliche Farbstoffe, femer synthetische Farbstoffe, wie z.B. anionische Farbstoffe, Metallkomplexfarbstoffe, Direktfarbstoffe, kationische Farbstoffe oder Schwefelfarbstoffe. Unter Farbstoffen sind auch Pigmente, d.h. in Wasser weitgehend unlösliche Farbstoffe zu verstehen.Suitable dyes are the leather dyes usually used, for example natural dyes, also synthetic dyes, such as e.g. anionic Dyes, metal complex dyes, direct dyes, cationic dyes or Sulfur dyes. Pigments are also included among dyes, i.e. largely in water to understand insoluble dyes.
Bei den lmprägniermitteln handelt es sich ebenfalls um die in der Lederindustrie verwendeten bekannten Mittel, z.B. um Mittel zum Schutz gegen Wasser, organische Lösungsmittel oder Öle oder gegen Schmutz, Mittel zur Verbesserung der Widerstandsfähigkeit gegen Abrieb, Scheuem oder andere mechanische Verletzungen, Mittel zur Verbesserung der Temperaturbeständigkeit oder Lichtechtheit und zur Verminderung der Entflammbarkeit oder um Antistatika.The impregnating agents are also those in the leather industry known means used, e.g. to means of protection against water, organic Solvents or oils or against dirt, means to improve the Resistance to abrasion, abrasion or other mechanical injuries, Means for improving the temperature resistance or light fastness and Flammability reduction or anti-static.
Geeignete Zurichtmittel sind z.B. Grundierungsmittel, wie Polyacrylate, Butadien-Mischpolymerisate oder Polyurethane, oder Appreturmittel, wie Casein-, Nitrocellulose- oder Polyurethanzubereitungen.Suitable dressing agents are e.g. Primers such as polyacrylates, butadiene copolymers or polyurethanes, or finishing agents, such as casein, nitrocellulose or Polyurethane formulations.
Als Zuricht-Hilfsmittel kommen die ebenfalls bekannten und in der Praxis gebrauchten Mittel in Frage, beispielsweise Penetratoren, Grundier- und Füllmittel, Klebeverhütungsmittel, Verdickungs- und Stabilisiermittel, Weichmacher, Mattierungsmittel, Griffmittel und Fixierungsmittel. As preparation aids come the well-known and used in practice into question, for example penetrators, primers and fillers, anti-adhesive agents, Thickening and stabilizing agents, plasticizers, matting agents, grip agents and Fixative.
Vorzugsweise handelt es sich um bei einer Temperatur unter 40 °C feste Mittel, es ist jedoch auch möglich, die erfindungsgemässen Mittel in Form von Lösungen, Dispersionen oder Emulsionen in einem geeigneten Lösungsmittel, vorzugsweise in Wasser, einzusetzen.It is preferably solid at a temperature below 40 ° C, it is however, the agents according to the invention are also possible in the form of solutions, dispersions or emulsions in a suitable solvent, preferably in water, use.
Besonders geeignete erfindungsgemässen Mittel zur Herstellung von Leder enthalten
Unter diesen sind solche Mittel besonders bevorzugt, die
Die Prozentangaben beziehen sich jeweils auf das Gesamtgewicht der Mittel zur Behandlung von Leder.The percentages relate to the total weight of the funds Leather treatment.
Die Herstellung der erfindungsgemässen Mittel geschieht auf an sich bekannte Art und Weise, beispielsweise dadurch, dass man ein Nachgerbmittel, ein Fettungsmittel und gegebenenfalls weitere Zusätze unverdünnt miteinander vermischt. In diesem Falle muss man das Nachgerbmittel und Fettungsmittel und die eventuell vorhandenen weiteren Zusätze so auswählen, dass die erhaltenen Mittel bei der Zugabe zu der mindestens 8fachen Menge Wasser bei 10 bis 60 °C homogene Mischungen ergeben.The agents according to the invention are produced in a manner known per se and Way, for example by adding a retanning agent, a fatliquor and if necessary, other additives are mixed undiluted. In this case the retanning agent and fatliquor and any further ones that may be present Select additives so that the agents obtained when added to the minimum 8 times the amount of water at 10 to 60 ° C give homogeneous mixtures.
Vorzugsweise setzt man jedoch Nachgerbmittel, Fettungsmittel und gegebenenfalls weitere Zusätze als Lösungen oder Suspensionen bzw. Dispersionen ein, vermischt sie und trocknet anschliessend. However, retanning agents, fatliquoring agents and optionally others are preferably used Additions as solutions or suspensions or dispersions, mixes them and then dries.
Bei den Lösungen, Suspensionen und Dispersionen dient vorzugsweise Wasser als Lösungsmittel, es kommen jedoch auch organische Lösungsmittel, beispielsweise ein- oder mehrwertige Alkohole oder Kohlenwasserstoffe in Betracht.In the case of the solutions, suspensions and dispersions, water preferably serves as Solvents, but there are also organic solvents, for example one or polyhydric alcohols or hydrocarbons.
Das Vermischen erfolgt beispielsweise bei einer Temperatur zwischen 10 und 60 °C, vorzugsweise jedoch bei Raumtemperatur, d.h. zwischen ca. 15 und 25 °C. Nach dem Vermischen muss vorzugsweise eine homogene Verteilung der Bestandteile der Suspensionen oder Dispersionen vorliegen, was erforderlichenfalls durch geeignete Massnahmen, wie z. B. Verwendung spezieller Rührer oder Ultraschallbehandlung, erreicht werden kann.Mixing takes place, for example, at a temperature between 10 and 60 ° C, but preferably at room temperature, i.e. between approx. 15 and 25 ° C. After this Mixing must preferably be a homogeneous distribution of the components of the Suspensions or dispersions are present, if necessary by suitable ones Measures such as B. Use of special stirrers or ultrasound treatment can be.
Die Trocknung erfolgt auf übliche Weise, sollte jedoch normalerweise unter Bedingungen durchgeführt werden, bei denen die homogene Verteilung der Bestandteile der Mischungen erhalten bleibt. Falls alle Komponenten gut in Wasser löslich oder leicht emulgierbar bzw. dispergierbar sind, spielt die Art der Trocknung keine Rolle.Drying is done in the usual way, but should normally be done under conditions be carried out in which the homogeneous distribution of the constituents of the mixtures preserved. If all components are readily soluble in water or easily emulsifiable or are dispersible, the type of drying does not matter.
Mit Vorzug verwendet man eine Methode, bei der die Trocknung sehr schnell erfolgt.It is preferable to use a method in which drying is very quick.
Vorzugsweise trocknet man durch Sprühtrocknung bei etwa 80 bis 140 °C, insbesondere bei 100 bis 120 °C.It is preferably dried by spray drying at about 80 to 140 ° C, especially at 100 to 120 ° C.
Es ist auch möglich, die Lösung, Suspension oder Dispersion auf einen vorgelegtes Trägermaterial, beispielsweise Natriumchlorid, Glaubersalz, Natriumformiat, Proteinpulver oder Stärke, zu sprühen und gleichzeitig oder anschliessend zu trocknen.It is also possible to put the solution, suspension or dispersion on a first Carrier material, for example sodium chloride, Glauber's salt, sodium formate, protein powder or starch to spray and dry at the same time or subsequently.
Man erhält nach diesen Verfahren die erfindungsgemässen Mittel in Form von Pulvem oder Granulaten, die in dieser Form zur Bereitung wässriger Flotten für die Lederherstellung eingesetzt werden können. Die Mittel sind nicht stäubend, lassen sich leicht homogen in Wasser verteilen und bleiben auch bei längerer Lagerung rieselfähig, auch bei Temperaturen bis ca. 40 °C. Wenn man kein Trägermaterial oder als solches eine nichtsalzartige Verbindung verwendet, lassen sich die erfindungsgemässen Mittel salzfrei oder salzarm herstellen, was bei der weiteren Bearbeitung, z.B. beim gleichzeitigen oder anschliessenden Färben oft von Vorteil ist und die Umwelt entlastet. The agents according to the invention are obtained in the form of powder or Granules in this form for the preparation of aqueous liquors for leather production can be used. The funds are not dusting, can be easily homogenized in Distribute water and remain free-flowing even after long storage, even with Temperatures up to approx. 40 ° C. If you don't have a carrier material or as such a non-salt one Used compound, the agents according to the invention can be salt-free or produce low in salt, which during further processing, e.g. with simultaneous or subsequent dyeing is often advantageous and relieves the environment.
Die erfindungsgemässen Mittel eignen sich zur Herstellung verschiedener Ledertypen, beispielsweise für vollnarbige, leicht oder stark nachgegerbte Leder oder Velourleder von Ziege, Schaf, Rind oder Schwein. Mit diesen Mitteln sind Leder für alle Verwendungszwecke herstellbar, beispielsweise Schuh-, Möbel-, Auto-, Bekleidungs- und Täschnerleder. Die erfindungsgemässen Mittel eignen sich ebenso für die Nachgerbung und Fettung von Pelzen, wobei die Haare weitgehend nicht beeinflusst werden.The agents according to the invention are suitable for producing various types of leather, for example for full-grain, slightly or heavily retanned leather or suede from Goat, sheep, beef or pork. With these means, leather is for everyone Usable uses, such as shoe, furniture, car, clothing and Bag leather. The agents according to the invention are also suitable for retanning and oiling of fur, whereby the hair is largely unaffected.
Die Herstellung der Leder kann in allen für die Nasszurichtung üblichen Maschinen durchgeführt werden, beispielsweise Fass, Dosamat, Gerbmaschine oder Mixer.The leather can be produced in all machines customary for wet finishing be carried out, for example barrel, Dosamat, tanning machine or mixer.
Die Herstellung erfolgt z.B. indem man vorgegerbtes Leder, beispielsweise Wetblue oder Wetwhite bei 10 - 50 °C in 50 - 300 % Wasser, bezogen auf das Gewicht des Substrates, vorlegt, dann 5 - 30 % des erfindungsgemässen Mittels hinzufügt und diese während 30 - 180 Minuten bei der genannten Temperatur unter Umwälzen einwirken lässt. Anschliessend setzt man gegebenenfalls 1 - 3 % Ameisensäure in zwei Teilen während 15 Minuten zu und setzt die Behandlung während 40 - 60 Minuten fort. Danach lässt man die Flotte ablaufen, spült während 5 - 10 Minuten mit 100 - 300 % Wasser, lässt die Spülflotte ablaufen und stellt auf übliche Weise fertig.The production takes place e.g. by using pre-tanned leather such as Wetblue or Wetwhite at 10 - 50 ° C in 50 - 300% water, based on the weight of the substrate, presents, then adds 5 - 30% of the agent according to the invention and this during 30 - Allows to act for 180 minutes at the stated temperature with circulation. Subsequently if necessary, 1-3% formic acid is added in two parts over 15 minutes and continue treatment for 40-60 minutes. Then let the fleet run off, rinses with 100 - 300% water for 5 - 10 minutes, drains the washing solution and completes in the usual way.
Falls man ein erfindungsgemässes Mittel eingesetzt hat, welches ausser Nachgerbmittel und Fettungsmittel keine weiteren Wirksubstanzen enthielt, so kann man die weiteren Behandlungsschritte, wie z.B. Neutralisation, Färben und Zurichten, auf übliche Weise durchführen.If you have used an agent according to the invention, which apart from retanning agent and fatliquor contained no other active substances, so you can the other Treatment steps, such as Neutralization, dyeing and dressing, in the usual way carry out.
Ein weiterer Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur
Herstellung von Leder oder Pelzen, dadurch gekennzeichnet, dass man vorgegerbte Leder
oder Pelze in wässriger Flotte mit einem Mittel behandelt, das
Man erhält nach dem erfindungsgemässen Verfahren Leder von gleicher oder besserer Qualität als von Leder, bei dessen Herstellung die Behandlung mit Nachgerbmittel und Fettungsmittel jeweils in getrennten Schritten durchgeführt wurde.Leather of the same or better quality is obtained by the process according to the invention Quality of leather, in the production of which the treatment with retanning agents and Fatliquor was carried out in separate steps.
Die nachfolgenden Beispiele erläutern die Erfindung, ohne sie darauf zu beschränken. Teile bedeuten Gewichtsteile und Prozente Gewichtsprozente. Die Temperaturen sind in °Celsius angegeben.The following examples illustrate the invention without restricting it. parts mean parts by weight and percentages by weight. The temperatures are in degrees Celsius specified.
Diese Mischung wird bei Normaldruck und 110 °C sprühgetrocknet. Man erhält ein Pulver, das sich für die Nasszurichtung von Wetblue und Wetwhite eignet, insbesondere für die Herstellung von Möbel- und Autopolsterleder sowie Schuhleder.This mixture is spray dried at normal pressure and 110 ° C. You get a powder which is suitable for wet dressing wetblue and wetwhite, especially for Manufacture of furniture and car upholstery leather and shoe leather.
Diese Mischung wird bei Normaldruck und 110 °C sprühgetrocknet. Man erhält ein Pulver, das sich für die Nasszurichtung von Wetblue und Wetwhite eignet, insbesondere für die Herstellung von Möbel- und Autopolsterleder sowie Schuhleder.This mixture is spray dried at normal pressure and 110 ° C. You get a powder which is suitable for wet dressing wetblue and wetwhite, especially for Manufacture of furniture and car upholstery leather and shoe leather.
Diese Mischung wird bei Normaldruck und 110 °C sprühgetrocknet. Man erhält ein Pulver, das sich für die Nasszurichtung von Wetblue und Wetwhite eignet, insbesondere für die Herstellung von Schuhoberleder.This mixture is spray dried at normal pressure and 110 ° C. You get a powder which is suitable for wet dressing wetblue and wetwhite, especially for Manufacture of upper leather.
Man gibt ein Stück Wetblue (Rind) im Fass in 180 % Wasser von 30°und setzt 1,5 % Natriumbicarbonat zu. Nach 10 Minuten fügt man 10 % des Mittels gemäss Beispiel 1 zu und behandelt 60 Minuten bei 30°. Dann gibt man noch 100 % Wasser zu und erhöht die Temperatur auf 60°. Innerhalb von 10 Minuten setzt man 2 % Ameisensäure in zwei Raten zu und behandelt weitere 30 Minuten. Dann lässt man die Flotte ab, spült während 5 Minuten mit 200 % kaltem Wasser und stellt auf übliche Weise fertig. Put a piece of wetblue (beef) in a barrel in 180% water at 30 ° and sit 1.5% sodium bicarbonate too. After 10 minutes, 10% of the agent according to Example 1 is added and treated for 60 minutes at 30 °. Then you add 100% water and increase the Temperature to 60 °. Within 10 minutes, 2% formic acid is added in two installments and treated for a further 30 minutes. Then let the fleet down, rinse during 5 Minutes with 200% cold water and finish in the usual way.
Das erhaltene Leder ist deutlich weicher als auf konventionelle Weise hergestelltes Leder, bei dessen Herstellung die Neutralisation, die Nachgerbung und die Fettung jeweils einzeln nacheinander durchgeführt werden. Zudem zeichnet es sich durch bessere Reissfestigkeit und niedrigere Foggingwerte aus, bei niedrigeren Herstellungskosten.The leather obtained is significantly softer than leather produced in a conventional manner, the neutralization, retanning and oiling in each case individually be carried out one after the other. It also has better tear resistance and lower fogging values at lower manufacturing costs.
Diese Mischung wird bei Normaldruck und 110 °C sprühgetrocknet.This mixture is spray dried at normal pressure and 110 ° C.
Arbeitet wie im Beispiel 4 beschrieben, verwendet jedoch anstelle des Mittels gemäss Beispiel 1 20 % der vorstehend beschriebenen Mischung, so erhält man egal schwarz gefärbtes Leder, das eine deutlich bessere Durchfärbung zeigt als ein auf konventionelle Weise hergestelltes Leder, bei dessen Herstellung die Neutralisation, die Nachgerbung, die Fettung und Färbung jeweils einzeln nacheinander durchgeführt werden. Works as described in example 4, but uses instead of the agent according to Example 1 20% of the mixture described above, so no matter black dyed leather, which shows a significantly better coloring than on conventional Leather made wisely, in the manufacture of which neutralization, retanning, Greasing and coloring are carried out one after the other.
Diese Mischung wird bei Normaldruck und 110 °C sprühgetrocknet. Man erhält ein Pulver, das sich für die Nasszurichtung von Wetblue und Wet white eignet, insbesondere für die Herstellung von Schuhoberleder.This mixture is spray dried at normal pressure and 110 ° C. You get a powder which is suitable for wet dressing of wetblue and wet white, especially for Manufacture of upper leather.
Man gibt ein Stück Wetblue (Rind) 1,9 mm gefalzt im Fass in 30 % Wasser von
30°und setzt 15 % des Mittels gemäss Beispiel 6 zu und behandelt 30 Minuten bei 30°.
Dann gibt man 3 % des Schwarzen Pulver-Farbstoffes C.I.Acid Black 210 zu und behandelt
90 Minuten bei 30 °.A piece of Wetblue (beef) 1.9 mm folded in a barrel in 30% water at 30 ° is added, and 15% of the agent according to Example 6 is added and treated at 30 ° for 30 minutes.
Then add 3% of the black powder dye CIAcid Black 210 and treat for 90 minutes at 30 °.
Danach gibt man noch 200 % Wasser zu und erhöht die Temperatur auf 60°. Innerhalb von 10 Minuten setzt man 1 % Ameisensäure zu und behandelt weitere 30 Minuten. Dann lässt man die Flotte ab, spült während 5 Minuten mit 200 % kaltem Wasser und stellt auf übliche Weise fertig.Then add 200% water and raise the temperature to 60 °. Within 10% 1% formic acid is added and treatment is continued for a further 30 minutes. Then lets the liquor is washed off, rinsed with 200% cold water for 5 minutes and set to normal Way done.
Das erhaltene Leder ist deutlich weicher als auf konventionelle Weise hergestelltes Leder, bei dessen Herstellung die Neutralisation, die Nachgerbung und die Fettung jeweils einzeln nacheinander durchgeführt werden.The leather obtained is significantly softer than leather produced in a conventional manner, the neutralization, retanning and oiling in each case individually be carried out one after the other.
Claims (27)
- A composition for the preparation of leather or pelts, which comprisesa) 10 - 80 percent by weight of a retanning agent andb) 5 - 50 percent by weight of a fatliquoring agent, andc) 5 - 50 percent by weight of further additives,
- A composition according to claim 1, which can be distributed homogeneously by customary incorporation by stirring into water which is at from 10 to 60 °C.
- A composition according to either of claims 1 and 2, which on addition to water forms micelles containing retanning agent and fatliquor agent.
- A composition according to any one of claims 1 to 3, which on incorporation by stirring into water gives a dispersion or suspension in which 50 % of the particles have a size below 15 µm.
- A composition according to any one of claims 1 to 3, which on incorporation by stirring into water gives a dispersion or suspension in which 90 % of the particles have a size below 40 µm.
- A composition according to any one of claims 1 to 5, which is solid at a temperature below 40 °C.
- A composition according to any one of claims 1 to 6, which comprises a neutralizing agent as further additive.
- A composition according to claim 7, which comprises as neutralizing agent alkali metal salts of inorganic or organic weak acids, aromatic sulfonic acids or aliphatic mono- or dicarboxylic acids.
- A composition according to claim 8, which comprises as neutralizing agent sodium or potassium bicarbonate, formate or acetate, oxalic acid, malonic acid, adipic acid or a condensed sulfonated phenol.
- A composition according to claim 9, which comprises as neutralizing agent sodium bicarbonate, sodium formate, acetic acid, adipic acid or a sulfonated diphenyl sulfone.
- A composition according to any one of claims 1 - 10, which comprises as retanning agent a vegetable tanning agent, an aromatic syntan, a resin tanning agent, a reactive tanning agent or a mineral tanning agent or polymeric tanning agent.
- A composition according to claim 11, which comprises as retanning agent a vegetable tanning agent, an aromatic syntan or a reactive tanning agent.
- A composition according to any one of claims 1 - 12, which comprises as fatliquoring agenta) a fatliquoring agent based on animal fats,b) a fatliquoring agent based on vegetable fats,c) a synthetic fatliquoring agent, ord) a mineral oil.
- A composition according to claim 13, wherein a fatliquoring agent is employed which is in a form modified by sulfating, sulfiting or the formation of sulfonic acids so that it is soluble or emulsifiable in water.
- A composition according to any one of claims 1 - 14, which comprises as further additive a carrier, a colorant, an impregnant, a dressing agent or a dressing auxiliary.
- A composition according to claim 15, which comprises as carrier sodium chloride, Glauber salt, sodium formate, protein powders or starch.
- A composition according to any one of claims 1 - 16, which comprises as further additive a colorant.
- A composition according to claim 17, which comprises as colorant a natural dye, a synthetic anionic or metal complex, direct or sulfur dye or a pigment.
- A composition according to any one of claims 1 - 18, comprisinga) 10 - 60 % by weight of a retanning agent,b) 10 - 45 % by weight of a fatliquoring agent,c) 10 - 40 % by weight of a neutralizing agent, andd) 0 - 40 % by weight of further additives.
- A solid composition according to claim 19, comprisinga) 20 - 60 % by weight of a retanning agent,b) 10 - 40 % by weight of a fatliquoring agent,c) 10 - 25 % by weight of a neutralizing agent, andd) 2 - 35 % by weight of further additives.
- A process for preparing a composition according to any one of claims 1 to 20, which comprises mixing a retanning agent, a fatliquoring agent and, if desired, further additives with one another in undiluted form.
- A process for preparing a solid composition according to any one of claims 1 to 20, which comprises employing a retanning agent, a fatliquoring agent and any other additives as solutions or suspensions, or else dispersions, mixing them with one another and then drying the mixture.
- A process according to claim 22, wherein, after mixing, the solution, suspension or dispersion is subjected to ultrasonic treatment.
- A process according to either of claims 22 and 23, wherein the drying process is carried out such that the solution, suspension or dispersion is dried without separating.
- A process according to any one of claims 22 to 24, wherein drying is carried out by spray drying.
- A process for the preparation of leather or pelts, which comprises treating pretanned leather or pelts in an aqueous liquor with a composition according to any one of claims 1 to 20.
- A process according to claim 26, wherein pretanned leathers or pelts are treated in an aqueous liquor which comprises micelles containing retanning agent and fatliquoring agent.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19653549 | 1996-12-20 | ||
DE1996153549 DE19653549A1 (en) | 1996-12-20 | 1996-12-20 | Composition for preparing leather and hides used for retanning and dubbing |
DE19746445 | 1997-10-21 | ||
DE1997146445 DE19746445A1 (en) | 1997-10-21 | 1997-10-21 | Composition for preparing leather and hides used for retanning and dubbing |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0849365A1 EP0849365A1 (en) | 1998-06-24 |
EP0849365B1 true EP0849365B1 (en) | 2003-08-20 |
Family
ID=26032583
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97810974A Expired - Lifetime EP0849365B1 (en) | 1996-12-20 | 1997-12-11 | Preparation agent for leather |
Country Status (11)
Country | Link |
---|---|
US (1) | US6033590A (en) |
EP (1) | EP0849365B1 (en) |
JP (1) | JPH10195500A (en) |
KR (1) | KR19980064329A (en) |
AR (1) | AR010810A1 (en) |
AT (1) | ATE247719T1 (en) |
AU (1) | AU733894B2 (en) |
BR (1) | BR9705614A (en) |
DE (1) | DE59710609D1 (en) |
PL (1) | PL323618A1 (en) |
TR (1) | TR199701669A1 (en) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19917736A1 (en) * | 1999-04-20 | 2000-10-26 | Zschimmer & Schwarz Gmbh & Co | Liquid, storage-and emulsion-stable composition for wet currying of leather or pelts has the starting materials for the dubbing component oxidized prior to further emulsifying reactions |
DE10105345A1 (en) * | 2000-07-14 | 2002-01-24 | Arconia Gmbh Chur | Composition for cleaning and disinfecting animal hair products, e.g. wool, pelts and furs, comprises a food preservative and a nontoxic acid |
EP1517999A1 (en) * | 2002-06-28 | 2005-03-30 | TFL Ledertechnik GmbH | Process and auxiliaries for the treatment of organically tanned leather |
DE10237259A1 (en) * | 2002-08-14 | 2004-02-26 | Basf Ag | Clay mineral giving specified particle size on stirring in water is used as a leather tanning agent, especially in combination with an organic tanning agent |
DE10250112A1 (en) * | 2002-10-28 | 2004-05-06 | Bayer Ag | Condensation product for giving in Fe-tanned leather |
DE10255095A1 (en) * | 2002-11-26 | 2004-06-03 | Basf Ag | Process for the manufacture of a semi-finished leather product |
WO2004067782A1 (en) * | 2003-01-28 | 2004-08-12 | Basf Aktiengesellschaft | Tanning agents and preservatives |
KR20050038356A (en) * | 2003-10-22 | 2005-04-27 | 제이알램스킨(주) | Method of making leather goods using ultrasound |
WO2005071118A1 (en) * | 2003-12-25 | 2005-08-04 | Council Of Scientific And Industrial Research | A process for making leather |
JP2005272725A (en) * | 2004-03-25 | 2005-10-06 | Takaban:Kk | Leather and method for producing the same |
US20060288494A1 (en) * | 2005-06-24 | 2006-12-28 | Wolverine World Wide, Inc. | Process for producing leather |
DE102005032585A1 (en) * | 2005-07-11 | 2007-01-25 | Basf Ag | Process for the production of leather |
JP4789552B2 (en) * | 2005-09-07 | 2011-10-12 | トヨタ自動車株式会社 | Method for manufacturing leather material |
DE102006029408A1 (en) * | 2006-06-23 | 2007-12-27 | Lanxess Deutschland Gmbh | Condensation products containing sulfonic or carboxylic acid groups and based on di-aldehyde and amino compounds, e.g. glutaraldehyde and melamine and-or urea, used for tanning leather and furs |
JP5172228B2 (en) | 2007-06-28 | 2013-03-27 | ミドリホクヨー株式会社 | leather |
JP4897649B2 (en) * | 2007-11-02 | 2012-03-14 | 佳裕 徳永 | Manufacturing method of embossed leather material |
US20110064959A1 (en) * | 2007-12-28 | 2011-03-17 | Midori Hokuyo Co., Ltd. | Low-voc leather |
WO2009084236A1 (en) * | 2007-12-28 | 2009-07-09 | Midori Hokuyo Co., Ltd. | Low voc leather |
KR101071337B1 (en) | 2009-12-03 | 2011-10-07 | 한국신발피혁연구소 | Method for manufacture of natural leather with black color using natural dyes |
JP2010138407A (en) * | 2010-02-16 | 2010-06-24 | Takaban:Kk | Leather, method of manufacturing the same and equipment for manufacturing the same |
NL2008666C2 (en) * | 2012-04-20 | 2013-10-23 | Stahl Int Bv | Composition and process for the retanning and fatliquoring of leather, and the leather prepared. |
RS55791B1 (en) | 2013-10-16 | 2017-08-31 | Balenciaga | Ecological tanning and dyeing process and product obtained |
CN104711382B (en) * | 2015-03-17 | 2016-11-30 | 峰安皮业股份有限公司 | A kind of manufacture method of waterproof and breathable leather |
CN105441601B (en) * | 2015-12-22 | 2017-12-26 | 峰安皮业股份有限公司 | A kind of production method of army and police's boots leather |
KR101957504B1 (en) * | 2017-11-02 | 2019-03-12 | (주)장원피혁 | A method for manufacturing a high-density slim type sports climbing natural leather upper and a natural leather upper for sports climbing manufactured by the method |
CN114561498A (en) * | 2022-02-24 | 2022-05-31 | 上海金狮化工有限公司 | Antistatic fatting agent, preparation method and production method of antistatic leather |
IT202200005300A1 (en) | 2022-03-17 | 2023-09-17 | Fgl Int S P A | Method of lubricating leather goods and lubricating product used in that method |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2056345A1 (en) * | 1970-11-17 | 1972-05-18 | Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen | Process for retanning and fatliquoring leather |
DE3238180C1 (en) * | 1982-10-15 | 1984-04-19 | Schill & Seilacher GmbH & Co, 7030 Böblingen | Process for greasing leather and furs |
SU1158586A1 (en) * | 1983-10-11 | 1985-05-30 | Vostoch Sibirsk Tekh Inst | Method of processing leather goods |
DE3419405A1 (en) * | 1984-05-24 | 1985-11-28 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING LEATHER AND FURS |
DE3444864A1 (en) * | 1984-12-08 | 1986-06-12 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR GREATING LEATHER AND FURS |
US5264000A (en) * | 1988-06-06 | 1993-11-23 | Ciba-Geigy Corporation | Aqueous solutions of synthetic tanning agents |
DE4121865A1 (en) * | 1991-07-02 | 1993-01-14 | Boehme Chem Fab Kg | Post-tanning, dyeing and dubbing of leather - by spraying without using treatment bath |
US5527360A (en) * | 1992-03-21 | 1996-06-18 | Basf Aktiengesellschaft | Fatliquoring, filling and hydrophobicizing leathers and furs |
EP0717114A3 (en) * | 1994-12-15 | 1996-08-21 | Ciba Geigy Ag | Aqueous composition for pretanning hides or retanning of leather |
-
1997
- 1997-12-10 PL PL97323618A patent/PL323618A1/en unknown
- 1997-12-11 EP EP97810974A patent/EP0849365B1/en not_active Expired - Lifetime
- 1997-12-11 DE DE59710609T patent/DE59710609D1/en not_active Expired - Lifetime
- 1997-12-11 AT AT97810974T patent/ATE247719T1/en not_active IP Right Cessation
- 1997-12-18 AR ARP970106003A patent/AR010810A1/en not_active Application Discontinuation
- 1997-12-18 BR BR9705614A patent/BR9705614A/en unknown
- 1997-12-19 US US08/994,879 patent/US6033590A/en not_active Expired - Lifetime
- 1997-12-19 JP JP9351218A patent/JPH10195500A/en active Pending
- 1997-12-19 TR TR97/01669A patent/TR199701669A1/en unknown
- 1997-12-19 KR KR1019970070393A patent/KR19980064329A/en not_active Application Discontinuation
- 1997-12-19 AU AU48513/97A patent/AU733894B2/en not_active Ceased
Also Published As
Publication number | Publication date |
---|---|
AU4851397A (en) | 1998-06-25 |
KR19980064329A (en) | 1998-10-07 |
ATE247719T1 (en) | 2003-09-15 |
MX9710304A (en) | 1998-08-30 |
BR9705614A (en) | 1999-03-09 |
AU733894B2 (en) | 2001-05-31 |
US6033590A (en) | 2000-03-07 |
EP0849365A1 (en) | 1998-06-24 |
DE59710609D1 (en) | 2003-09-25 |
JPH10195500A (en) | 1998-07-28 |
PL323618A1 (en) | 1998-06-22 |
AR010810A1 (en) | 2000-07-12 |
TR199701669A1 (en) | 2001-10-22 |
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