EP1118682B1 - Preparations of tanning/ retanning agents - Google Patents
Preparations of tanning/ retanning agents Download PDFInfo
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- EP1118682B1 EP1118682B1 EP01100041A EP01100041A EP1118682B1 EP 1118682 B1 EP1118682 B1 EP 1118682B1 EP 01100041 A EP01100041 A EP 01100041A EP 01100041 A EP01100041 A EP 01100041A EP 1118682 B1 EP1118682 B1 EP 1118682B1
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- Prior art keywords
- compound
- preparations according
- solid preparations
- tanning
- acid
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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
- C14C3/08—Chemical tanning by organic agents
- C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
- C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated
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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
Definitions
- the invention relates to solid tannin / retanning preparations, a method for their production, their use for tanning and retanning as well as with them tanned and retanned leather and furs.
- Retanning means that Aftertreatment of pre-tanned (generally chrome-tanned) leather to Color, levelness, softness, fullness and behavior against water (hydrophobicity) to optimize and fix tannins.
- pre-tanned generally chrome-tanned
- Tanning, retanning and dyeing in particular are usually carried out in different ways so-called tanning drums using aqueous tanning / retanning solutions or dispersions or dye solutions carried out.
- Most of the tannins and tanning agents used are powdered Solid added to the tanning tanks (fleets), which makes handling easy and minimal storage space guaranteed.
- To rationalize these steps have been mixtures of various powdered tannins in the past and tanning aids are manufactured, with which the tanning process by saving of path and add operations to be simplified.
- EP-A 849 365 describes a solid agent for the simultaneous retanning and greasing of Leather described, which in addition to ordinary powdered, water-soluble After-tanning agents are other normally liquid or waxy, non-aqueous oils and contains fats.
- retanning agents for example the polymeric retanning agents, where 10 to 80% by weight of the monomer units carry one or more C 2 -C 40 -alkyl radicals and this polymer contains 1 to 10 mol / kg of acid groups, in particular carboxylic acid and / or carboxylate groups so far, however, mostly added to the aqueous liquors in the form of their aqueous solutions or suspensions. Attempts to obtain equivalent powdered dosage forms by simply drying failed. The products obtained in this way often have poor redispersibility or other disadvantageous effects of the solid forms.
- the solid preparations according to the invention are preferably in the form of powder or Granules before.
- Granules are in particular those with an average grain size from 0.5 to 5 mm is preferred.
- the solid preparations according to the invention in the form Their granules are also not dusty and very free-flowing.
- the preparations according to the invention are also in a preferred embodiment completely soluble or emulsifiable in water, the solubility or emulsifiability is preferably more than 50 g / l at 20 ° C.
- the preparations according to the invention preferably contain, based on the preparation 25 to 95% by weight at least one compound A), 5 to 50% by weight at least one compound B) and 0 to 50% by weight one or more additives C).
- the preparations according to the invention containing are preferred 30 to 70% by weight at least one compound A), 15 to 40% by weight at least one compound B) and 0 to 40% by weight further additives C), 5 to 20% by weight of a neutralizing agent being preferred as additive C).
- Preferred compounds A) are tannins, in particular solid tannins, which are selected with particular preference from the group of mineral tannins, vegetable tannins, syntans and resin tannins.
- mineral tanning agents are e.g. Salts of chrome, aluminum or zirconium, but especially trivalent chromium compounds such as chromium sulfate, basic To name chromium sulfate or chromium acetate.
- Vegetable tanning agents are generally understood to mean tanning agents which are caused by Extraction, drying and optionally post-treatment from various Plants or parts of plants are obtained, e.g. Chestnut, sweet chestnut, Mimosa, Quebracho, Tara, or similar substances, the so-called hydrolyzable or contain condensed tannins (see e.g. Reich, G. Theory and practice of organic Tanning agents, part 1: general principles and natural organic tanning agents, The leather, 1996, 74-83).
- the synthetic organic tannins also called syntans, are mostly through Sulfonation or sulfomethylation solubilized aldehyde condensation products aromatic base, in particular of phenol, cresol, naphthalene and Naphthol, Biaryl, Biarylether and Biarylsulfone.
- Condensates from naphthalenesulfonic acids, phenolsulfonic acid, diphenyl sulfones or sulfonated diaryl ethers with formaldehyde and / or urea.
- Such condensates are known, for example, from Herfeld (editor) "Bibliothek des Leders", vol. 3, pages 53 to 59, Umschau-Verlag 1984 or Reich, G. Theory and Practice of organic tanning agents, part 2: synthetic organic tanning agents, leather, 1996, 157-171 and can according to the references given there described methods are produced.
- cationic ones are preferred Condensation products of nitrogen-containing compounds, especially urea, dicyanamide or melamine with formaldehyde and their anionic reaction products with compounds such as phenol, sulfonated aromatics or sulfites Roger that.
- the preparations according to the invention contain in a preferred embodiment as compound A) aromatic syntans from the condensation of naphthalenesulfonic acid, Phenolsulfonic acid, bishydroxyphenyl sulfone and / or ditolyl ether sulfonic acids with formaldehyde and / or urea.
- Tanning should be preferred under treatment in water at 20-50 ° C to be understood under conditions and with amounts as used in the Craftsman trained specialist for the respective groups of substances as typical.
- the regulations in Herfeld (ed.) "library des Leders ", Umschau Verlag, 1984, Vol. 3, S 306-314, Examples 10-16 subsequent measurement of the shrinkage temperature is carried out according to that in DIN EN 12993 given method.
- Polymeric retanning agents from the class are preferably used as compound B) of polyacrylates or polyaspartic acids, but especially polyaspartic acids.
- Preferred preparations are also those in which the polymeric compound B) is selected from the group of poly (meth) acrylates and poly (meth) acrylate copolymers (B 1) or polyaspartic acids (B 2).
- Particularly preferred compounds from the group of poly (meth) acrylates and poly (meth) acrylate copolymers (B 1) are obtained, for. B. by polymerization of hydrophilic monomers such as (meth) acrylic acid, maleic acid or acrylic amides with (C 1 - C 2 ) amine constituents with 10-80% by weight of hydrophobic monomers such as alkenes, allyl esters, (meth) acrylic acid esters or acrylic acid amides Amine constituents, each with a chain length of (C 3 - C 40 ), or by polymerizing monomers such as (meth) acrylic acid, maleic anhydride or (meth) acrylic acid esters with (C 1 - C 2 ) alcohol components and subsequent partial Esterification or transesterification with (C 2 - C 40 ) alcohols.
- hydrophilic monomers such as (meth) acrylic acid, maleic acid or acrylic amides with (C 1 - C 2 ) amine constituents
- hydrophobic monomers such as alken
- Particularly preferred compounds from the group of polyaspartic acids (B 2) are e.g. B. the reaction products of polysuccinimide with 0.10 - 0.80 molar equivalents of amines or alcohols (C 2 - C 40 ) and subsequent partial neutralization with inorganic bases such as sodium hydroxide or potassium hydroxide.
- the polymeric compounds B) average molecular weight of less than 100,000, especially smaller 20,000 g / mol.
- the polymeric compounds B) common that they are not used as a solid, anhydrous preparation can be, because after removal of the solvent z. B. no longer redispersible or are not stable in storage.
- compositions according to the invention can of course also be used for other purposes Contain additives C).
- additives C Contain additives C.
- neutralizing agents Dispersants, defoamers, water repellents or dyeing aids in question.
- Alkali salts of aromatic for example, can be used as neutralizing agents Sulphonic acids, weak inorganic acids or mono- or dicarboxylic acids be used.
- the neutralizing agents are preferred in an amount of 5 up to 20 wt .-%, based on the solid preparation, used.
- a very particularly preferred preparation contains e.g. B. 30 - 65 wt .-% of aromatic Syntanen A) in a mixture with 10 - 40 wt .-% of neutralizing and dispersing additives C) and 15-25% by weight of a polymeric retanning agent B) based on polyaspartic acid.
- This preparation is preferably as Granules before.
- Another very particularly preferred preparation contains 40-70% by weight a mixture of trivalent chromium salts, aromatic syntans and Resin tannins as compound A), 15-30% by weight of neutralizing additives C) and 15-40% by weight of a polymeric retanning agent B) from the group the poly (meth) acrylates or the polyaspartic acids. Get the percentages each on the preparation.
- a preparation containing 20-40% by weight of aromatic is also preferred Syntanen, 20 - 40 wt .-% of resin tanning agents and 30 - 40 wt .-% of neutralizing and dispersing additives with the help of 10 - 25 % By weight of a polymeric retanning agent B).
- the preparations mentioned are low in dust and free-flowing.
- the present invention also relates to a method for producing the invention Preparations that are characterized by the fact that one can connect A) optionally in a mixture with C) an aqueous solution and / or suspension of B) and, if necessary, during or after the Adding B) dries.
- Compound B) is preferably added a solid form of the compounds A) and optionally C). Especially done the addition by spraying on an aqueous solution or suspension of B) within a mixer.
- the mixture obtained can initially have pasty shapes accept.
- the during or after the addition of the aqueous Solution / suspension of B) subsequent drying is preferably carried out 20 to 200 ° C, especially at 20 to 105 ° C, most preferably at 50 to 100 ° C.
- the method according to the invention is also very particularly preferred, if the additions of the polymeric compound B) in an aqueous solution or aqueous suspension with a solids content of B) of 5 to 60%, in particular 10 to 50% is done.
- the invention further relates to the use of the preparations according to the invention for tanning and retanning pretreated hides or skins in water Fleet.
- it is preferred to use the preparations according to the invention Manufacture leather or fur to use by pre-tanning leather or furs in an aqueous liquor with the preparations according to the invention treated.
- Leather or furs that are produced are therefore also part of the invention have been using the preparations according to the invention as Tanning or retanning agents or those obtainable through the use according to the invention.
- the leathers according to the invention are produced by using a commercial tanning equipment such as a tanning drum, blender or Dosamat pickled pellets with 6-10% by weight of the product according to the invention Tanned 20 to 45 ° C. There are no further addition steps during the tanning process necessary.
- the tanned leather is washed and aftertreated in the usual manner, retanning and greasing are eliminated or significantly reduced Way can be done.
- commercially available wet blue is applied set a pH of about 3.5 and then in an aqueous liquor with 10-15 % By weight of the agent according to the invention retanned.
- the leather treated in this way can are processed further in the customary manner, with no subsequent greasing or can be carried out in a significantly reduced form.
- Naphthalene is sulfonated with 1.4 molar equivalents of H 2 SO 4 at 145 ° C for 2 hours.
- a mixture of 1000 g of the naphthalenesulfonic acids thus obtained, 800 g of bishydroxyphenyl sulfone and 250 ml of 37% by weight formaldehyde solution is condensed at 100-120 ° C. for 3 hours.
- the product obtained is adjusted to pH 3.5 and an acid number of 80 with sodium hydroxide solution and phthalic acid and spray-dried.
- shrinking temperatures of the leather obtained of 72-78 ° C. can be achieved.
- Phenol is sulfonated with 0.88 molar equivalents of H 2 SO 4 at 100 - 180 ° C.
- the resulting mixture of phenolsulfonic acid and bishydroxyphenylsulfone is neutralized with sodium hydroxide solution and then condensed with 0.44 molar equivalents of formaldehyde at 100-120 ° C.
- the raw condensate is adjusted to pH 3.7 and an acid number of 80 with glutaric acid and spray-dried.
- the leather's shrinking temperatures of 72 - 80 ° C can be achieved.
- Naphthalene is sulfonated with 1.4 mol H 2 SO 4 at 145 ° C. for 3 hours, condensed with 0.66 mol formaldehyde for 3 hours, cooled, adjusted to pH 3.5 and an acid number of 50 with sodium hydroxide solution and glutaric acid and spray-dried.
- leather shrink temperatures of 68 - 72 ° C can be achieved.
- Synthetic tanning agent A IV is a synthetic tanning agent A IV:
- Liquid, polymeric retanning agent B I Liquid, polymeric retanning agent B I:
- a solution of 1000 g maleic anhydride, 800 g diethylene glycol and 800 g ammonia solution (25%) is condensed in 4 hours at an increasing temperature of 60 - 145 ° C and then volatile components are distilled off. It is reacted with 700 g of hydrogenated tallow fatty amine for 6 hours, cooled to 110 ° C. and mixed with 170 g of oleic acid and 10 g of a silicone-containing defoamer.
- the hot reaction product is dispersed in 3 l of a 2.5% by weight ethanolamine solution, neutralized with sodium hydroxide solution and bleached with hydrogen peroxide. (see DE-A 19 959 949, component B 2 (PAS 1)).
- Liquid, polymeric retanning agent B II Liquid, polymeric retanning agent B II:
- Liquid, polymeric retanning agent B III Liquid, polymeric retanning agent B III:
- naphthalene 1000 g is sulfonated at 140-145 ° C. with 3 molar equivalents of H 2 SO 4 for 8 hours, adjusted to pH 7 with sodium hydroxide solution and the crude product mixture is spray-dried.
- Tl mean parts by weight.
- 20 parts of synthetic tanning agent AI, 10 parts of synthetic tanning agent A III, 20 parts of synthetic tanning agent A IV, 40 parts of additive C II and 10 parts of NaHCO 3 are mixed homogeneously at room temperature.
- 50 parts of polymeric tanning agent B II are continuously added at 60 ° C. in a mixed agglomeration apparatus.
- a free-flowing, storage-stable granulate is obtained which is soluble in water at room temperature without residue.
- Skin (beef, split thickness 2.5 mm) is decalcified, stained and in the usual way with a pimple made of 6% table salt, 0.5% formic acid and 1.0% sulfuric acid adjusted to pH 2.8. At room temperature, 9% of a product is added Example 11 and tanned for 2 hours at room temperature. Then the skin Moved overnight every 60 min for 5 min and the temperature slowly to 45 ° C raised. The fleet is drained, the leather washed, and to normal business Retanned, dyed, greased and finished.
- the leather obtained is softer and softer than commercially available comparison products has better scar strength, the coloring is more level.
- Wet Blue (beef, gap thickness 1.1 mm) is in the barrel at 35 ° C in 100% liquor with 7% of a product moved according to Example 12 for 2 hours. You wash, grease 50 ° C in 100% liquor with 7% of a commercially available synthetic fat, fixed by adding 2% formic acid a little at a time and switching to normal operating conditions Way done.
- wet blue (beef, fold thickness 1.5 mm) is in the barrel by treatment with oxalic acid in 200% liquor adjusted to pH 3.5 and the liquor drained. Then you give at 40 ° C 150% water and 12% of an agent according to Example 15. After 60 minute 1% dye is added and dyed at 50 ° C for 90 min. You fixate through portionwise addition of formic acid, drains the liquor, washes and makes that leather finished in the usual way.
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Description
Die Erfindung betrifft feste Gerbstoff-/Nachgerbstoffpräparationen, ein Verfahren zu ihrer Herstellung, ihre Verwendung zum Gerben und Nachgerben sowie damit gegerbte und nachgegerbte Leder und Pelze.The invention relates to solid tannin / retanning preparations, a method for their production, their use for tanning and retanning as well as with them tanned and retanned leather and furs.
Die Herstellung von Leder und Pelzen aus Häuten und Fellen verläuft gewöhnlich in mehreren Schritten. Nach den vorbereitenden Arbeiten der Wasserwerkstatt, wie Enthaaren, Entfleischen, Entkälken und Beizen besteht eine typische Abfolge aus Gerbung, Nachgerbung, Färbung, Fettung und Zurichtung. Die einzelnen Arbeitsschritte lassen sich dabei noch in weitere Untereinheiten aufteilen.The production of leather and furs from hides and skins usually takes place in several steps. After the preparatory work of the water workshop how Dehairing, meat removal, descaling and pickling consists of a typical sequence Tanning, retanning, coloring, greasing and dressing. The individual work steps can be divided into further subunits.
Während die Gerbung zu einer Erhöhung der Schrumpftemperatur des Leders führt, hat die Nachgerbung darauf kaum Einfluss. Unter "Nachgerbung" versteht man die Nachbehandlung von vorgegerbtem (im allgemeinen chromgegerbtem) Leder, um Farbe, Egalität, Weichheit, Fülle sowie das Verhalten gegen Wasser (Hydrophobie) zu optimieren und Gerbstoffe zu fixieren.While the tanning process increases the leather's shrinking temperature, retanning has hardly any influence on it. "Retanning" means that Aftertreatment of pre-tanned (generally chrome-tanned) leather to Color, levelness, softness, fullness and behavior against water (hydrophobicity) to optimize and fix tannins.
Besonders die Gerbung, Nachgerbung und Färbung werden dabei gewöhnlich in verschiedenen sogenannten Gerbfässern unter Verwendung wässriger Gerbstoff-/ Nachgerbstoff-Lösungen oder -Dispersionen respektive Farbstofflösungen durchgeführt. Ein Großteil der verwendeten Gerbstoffe und Gerbereihilfsmittel wird dabei als pulverförmiger Feststoff den Gerbfässern (Flotten) zugesetzt, was einfaches Handling und minimalen Lagerraum garantiert. Um diese Arbeitsschritte zu rationalisieren wurden in der Vergangenheit Mischungen verschiedener pulverförmiger Gerbstoffe und Gerbereihilfsmittel hergestellt, mit denen der Gerbvorgang durch Einsparung von Wege-und Zugabeoperationen vereinfacht werden soll.Tanning, retanning and dyeing in particular are usually carried out in different ways so-called tanning drums using aqueous tanning / retanning solutions or dispersions or dye solutions carried out. Most of the tannins and tanning agents used are powdered Solid added to the tanning tanks (fleets), which makes handling easy and minimal storage space guaranteed. To rationalize these steps have been mixtures of various powdered tannins in the past and tanning aids are manufactured, with which the tanning process by saving of path and add operations to be simplified.
In EP-A 849 365 ist ein festes Mittel zum gleichzeitigen Nachgerben und Fetten von Ledern beschrieben, welches neben gewöhnlichen pulverförmigen, wasserlöslichen Nachgerbstoffen weitere normalerweise flüssige oder wachsartige, nichtwässrige Öle und Fette enthält.EP-A 849 365 describes a solid agent for the simultaneous retanning and greasing of Leather described, which in addition to ordinary powdered, water-soluble After-tanning agents are other normally liquid or waxy, non-aqueous oils and contains fats.
Einige der Nachgerbstoffe beispielsweise die polymeren Nachgerbstoffe, wobei 10 bis 80 Gew.-% der Monomereinheiten einen oder mehrere C2-C40-Alkylreste tragen und dieses Polymer 1 bis 10 mol/kg Säuregruppen, insbesondere Carbonsäure- und/oder Carboxylatgruppen enthält, wurden bislang allerdings meist in Form ihrer wässrigen Lösungen oder Suspensionen den wässrigen Flotten zugesetzt. Versuche, äquivalente pulverförmige Darreichungsformen durch einfaches Trocknen zu gewinnen, scheiterten. Die so erhaltenen Produkte besitzen nicht selten eine schlechte Redispergierbarkeit bzw. andere nachteilige Effekte der festen Formen.Some of the retanning agents, for example the polymeric retanning agents, where 10 to 80% by weight of the monomer units carry one or more C 2 -C 40 -alkyl radicals and this polymer contains 1 to 10 mol / kg of acid groups, in particular carboxylic acid and / or carboxylate groups so far, however, mostly added to the aqueous liquors in the form of their aqueous solutions or suspensions. Attempts to obtain equivalent powdered dosage forms by simply drying failed. The products obtained in this way often have poor redispersibility or other disadvantageous effects of the solid forms.
Überraschend wurden nun feste Präparationen gefunden, enthaltend
- wenigstens eine Verbindung A), die in der Lage ist, die Schrumpfungstemperatur einer ungegerbten Blöße um wenigstens 10°C zu erhöhen, indem man die Blöße mit einer Verbindung A) in Wasser bei einer Temperatur von 20 bis 50°C behandelt,
- wenigstens eine davon verschiedene polymere Verbindung B), wobei 10 bis 80 Gew.-% der Monomereinheiten einen oder mehrere C2-C40-Alkylreste tragen und das Polymer B) 1 bis 10 mol/kg Säuregruppen, insbesondere Carbonsäure- und/oder Carboxylatgruppen enthält und gegebenenfalls
- weitere Zusatzstoffe C).
- at least one compound A) capable of increasing the shrinkage temperature of an untanned pelt by at least 10 ° C by treating the pelt with a compound A) in water at a temperature of 20 to 50 ° C,
- at least one different polymeric compound B), 10 to 80% by weight of the monomer units carrying one or more C 2 -C 40 -alkyl radicals and polymer B) 1 to 10 mol / kg of acid groups, in particular carboxylic acid and / or carboxylate groups contains and if necessary
- further additives C).
Die erfindungsgemäßen festen Präparationen liegen vorzugsweise als Pulver oder Granulat vor. Als Granulate sind insbesondere solche mit einer mittleren Korngröße von 0,5 bis 5 mm bevorzugt. Die erfindungsgemäßen festen Präparationen in Form ihrer Granulate sind zudem nicht staubend und sehr rieselfähig. The solid preparations according to the invention are preferably in the form of powder or Granules before. Granules are in particular those with an average grain size from 0.5 to 5 mm is preferred. The solid preparations according to the invention in the form Their granules are also not dusty and very free-flowing.
Die erfindungsgemäßen Präparationen sind darüberhinaus in einer bevorzugten Ausführungsform in Wasser rückstandslos löslich oder emulgierbar, wobei die Löslichkeit bzw. Emulgierbarkeit vorzugsweise bei 20°C mehr als 50 g/l beträgt.The preparations according to the invention are also in a preferred embodiment completely soluble or emulsifiable in water, the solubility or emulsifiability is preferably more than 50 g / l at 20 ° C.
Bevorzugt enthalten die erfindungsgemäßen Präparationen, bezogen auf die Präparation
Bevorzugt sind allerdings die erfindungsgemäßen Präparationen, enthaltend
Als Mineralgerbstoffe sind z.B. Salze von Chrom, Aluminium oder Zirkonium, besonders aber Verbindungen des dreiwertigen Chromes wie Chromsulfat, basisches Chromsulfat oder Chromacetat zu nennen.As mineral tanning agents are e.g. Salts of chrome, aluminum or zirconium, but especially trivalent chromium compounds such as chromium sulfate, basic To name chromium sulfate or chromium acetate.
Unter Vegetabilgerbstoffen werden im allgemeinen Gerbstoffe verstanden, die durch Extraktion, Trocknung und gegebenenfalls Nachbehandlung aus verschiedenen Pflanzen oder Pflanzenteilen erhalten werden wie z.B. Kastanie, Edelkastanie, Mimosa, Quebracho, Tara, oder ähnliche Stoffe, die sogenannte hydrolysierbare oder kondensierte Tannine enthalten (siehe z.B. Reich, G. Theorie und Praxis der organischen Gerbstoffe, Teil 1: allgemeine Grundlagen und natürliche organische Gerbstoffe, Das Leder, 1996, 74-83).Vegetable tanning agents are generally understood to mean tanning agents which are caused by Extraction, drying and optionally post-treatment from various Plants or parts of plants are obtained, e.g. Chestnut, sweet chestnut, Mimosa, Quebracho, Tara, or similar substances, the so-called hydrolyzable or contain condensed tannins (see e.g. Reich, G. Theory and practice of organic Tanning agents, part 1: general principles and natural organic tanning agents, The leather, 1996, 74-83).
Die synthetischen organischen Gerbstoffe, auch Syntane genannt, sind meist durch Sulfonierung oder Sulfomethylierung löslich gemachte Aldehyd-Kondensationsprodukte aromatischer Grundkörper, insbesondere von Phenol, Kresol, Naphthalin und Naphthol, Biaryl, Biarylether und Biarylsulfone. Besonders bevorzugt sind Kondensate aus Naphthalinsulfonsäuren, Phenolsulfonsäure, Diphenylsulfonen oder sulfonierten Diarylethern mit Formaldehyd und/oder Harnstoff. Solche Kondensate sind bekannt beispielsweise aus Herfeld (Herausgeber) "Bibliothek des Leders", Bd. 3, Seite 53 bis 59, Umschau-Verlag 1984 oder Reich, G. Theorie und Praxis der organischen Gerbstoffe, Teil 2: Synthetische organische Gerbstoffe, Das Leder, 1996, 157-171 und können nach den dort in den angegebenen Referenzen beschriebenen Verfahren hergestellt werden.The synthetic organic tannins, also called syntans, are mostly through Sulfonation or sulfomethylation solubilized aldehyde condensation products aromatic base, in particular of phenol, cresol, naphthalene and Naphthol, Biaryl, Biarylether and Biarylsulfone. Are particularly preferred Condensates from naphthalenesulfonic acids, phenolsulfonic acid, diphenyl sulfones or sulfonated diaryl ethers with formaldehyde and / or urea. Such condensates are known, for example, from Herfeld (editor) "Bibliothek des Leders", vol. 3, pages 53 to 59, Umschau-Verlag 1984 or Reich, G. Theory and Practice of organic tanning agents, part 2: synthetic organic tanning agents, leather, 1996, 157-171 and can according to the references given there described methods are produced.
Unter den sogenannten Harzgerbstoffen werden vorzugsweise kationische Kondensationsprodukte stickstoffhaltiger Verbindungen, insbesondere Harnstoff, Dicyanamid oder Melamin mit Formaldehyd sowie deren anionische Umsetzungsprodukte mit Verbindungen wie Phenol, sulfonierten Aromaten oder Sulfiten verstanden.Among the so-called resin tanning agents, cationic ones are preferred Condensation products of nitrogen-containing compounds, especially urea, dicyanamide or melamine with formaldehyde and their anionic reaction products with compounds such as phenol, sulfonated aromatics or sulfites Roger that.
Die erfindungsgemässen Präparationen enthalten in einer bevorzugten Ausführungsform als Verbindung A) aromatische Syntane aus der Kondensation von Naphthalinsulfonsäure, Phenolsulfonsäure, Bishydroxyphenylsulfon und/oder Ditolylethersulfonsäuren mit Formaldehyd und/oder Harnstoff.The preparations according to the invention contain in a preferred embodiment as compound A) aromatic syntans from the condensation of naphthalenesulfonic acid, Phenolsulfonic acid, bishydroxyphenyl sulfone and / or ditolyl ether sulfonic acids with formaldehyde and / or urea.
In einer weiteren besonders bevorzugten Ausführungsform werden als Verbindung A) 40 - 90 Gew.-% solcher Syntane aus der Kondensation von Naphthalinsulfonsäure, Phenolsulfonsäure, Bishydroxyphenylsulfon oder Ditolylethersulfonsäuren mit Formaldehyd und/oder Harnstoff in Kombination mit mineralischen Gerbstoffen, besonders Verbindungen des dreiwertigen Chromes wie Chromsulfat oder Chromacetat und/oder Harzgerbstoffen eingesetzt.In a further particularly preferred embodiment, the connection A) 40-90% by weight of such syntans from the condensation of naphthalenesulfonic acid, Phenolsulfonic acid, bishydroxyphenyl sulfone or ditolyl ether sulfonic acids Formaldehyde and / or urea in combination with mineral tannins, especially trivalent chromium compounds such as chromium sulfate or chromium acetate and / or resin tanning agents used.
Unter der Behandlung in Wasser bei 20-50°C sollen Gerbungen vorzugsweise verstanden werden, unter Bedingungen und mit Einsatzmengen wie sie ein im Handwerk ausgebildeter Fachmann für die jeweiligen Stoffgruppen als typisch kennt. Als Anhaltspunkte dafür seien z.B. die Vorschriften in Herfeld (Hrsg.) "Bibliothek des Leders", Umschau Verlag, 1984, Bd. 3, S 306-314, Beispiele 10-16, genannt. Die anschließende Messung der Schrumpfungstemperatur erfolgt nach der in der DIN EN 12993 gegebenen Methode.Tanning should be preferred under treatment in water at 20-50 ° C to be understood under conditions and with amounts as used in the Craftsman trained specialist for the respective groups of substances as typical. As a guide, e.g. the regulations in Herfeld (ed.) "library des Leders ", Umschau Verlag, 1984, Vol. 3, S 306-314, Examples 10-16 subsequent measurement of the shrinkage temperature is carried out according to that in DIN EN 12993 given method.
Als Verbindung B) werden vorzugsweise polymere Nachgerbstoffe aus der Klasse der Polyacrylate oder Polyasparaginsäuren, besonders aber Polyasparaginsäuren verwendet.Polymeric retanning agents from the class are preferably used as compound B) of polyacrylates or polyaspartic acids, but especially polyaspartic acids.
Bevorzugte Präparationen sind ebenfalls solche, bei denen die polymere Verbindung B) ausgewählt wird aus der Gruppe der Poly(meth)acrylate und Poly(meth)acrylat-Copolymerisate (B 1) oder Polyasparaginsäuren (B 2).Preferred preparations are also those in which the polymeric compound B) is selected from the group of poly (meth) acrylates and poly (meth) acrylate copolymers (B 1) or polyaspartic acids (B 2).
Besonders bevorzugte Verbindungen aus der Gruppe der Poly(meth)acrylate und Poly(meth)acrylat-Copolymerisate (B 1) werden erhalten z. B. durch Polymerisation von hydrophilen Monomeren wie (Meth)acrylsäure, Maleinsäure oder Acrylsäureamiden mit (C1 - C2) Amin-Bestandteilen mit 10 - 80 Gew.-% von hydrophoben Monomeren wie Alkenen, Allylestern, (Meth)Acrylsäureestern oder Acrylsäureamiden mit Amin-Bestandteilen, jeweils mit einer Kettenlänge von (C3 - C40), oder durch Polymerisation von Monomeren wie (Meth)Acrylsäure, Maleinsäureanhydrid oder (Meth)Acrylsäure-Estern mit (C1 - C2) Alkohol-Komponenten und anschließende partielle Veresterung oder Umesterung mit (C2 - C40) Alkoholen.Particularly preferred compounds from the group of poly (meth) acrylates and poly (meth) acrylate copolymers (B 1) are obtained, for. B. by polymerization of hydrophilic monomers such as (meth) acrylic acid, maleic acid or acrylic amides with (C 1 - C 2 ) amine constituents with 10-80% by weight of hydrophobic monomers such as alkenes, allyl esters, (meth) acrylic acid esters or acrylic acid amides Amine constituents, each with a chain length of (C 3 - C 40 ), or by polymerizing monomers such as (meth) acrylic acid, maleic anhydride or (meth) acrylic acid esters with (C 1 - C 2 ) alcohol components and subsequent partial Esterification or transesterification with (C 2 - C 40 ) alcohols.
Besonders bevorzugte Verbindungen aus der Gruppe der Polyasparaginsäuren (B 2) sind z. B. die Umsetzungsprodukte von Polysuccinimid mit 0.10 - 0.80 Moläquivalenten an Aminen oder Alkoholen (C2 - C40) und anschliessender partieller Neutralisation mit anorganischen Basen wie Natriumhydroxid oder Kaliumhydroxid.Particularly preferred compounds from the group of polyaspartic acids (B 2) are e.g. B. the reaction products of polysuccinimide with 0.10 - 0.80 molar equivalents of amines or alcohols (C 2 - C 40 ) and subsequent partial neutralization with inorganic bases such as sodium hydroxide or potassium hydroxide.
In einer bevorzugten Ausführungsform besitzen die polymeren Verbindungen B) ein mittleres Molekulargewicht von kleiner 100.000, insbesondere von kleiner 20.000 g/mol.In a preferred embodiment, the polymeric compounds B) average molecular weight of less than 100,000, especially smaller 20,000 g / mol.
In einer weiteren besonders bevorzugten Ausführungsform ist den polymeren Verbindungen B) gemeinsam, dass sie nicht als feste, wasserfreie Präparation eingesetzt werden können, da sie nach Entfernung des Lösungsmittels z. B. nicht mehr redispergierbar oder nicht lagerstabil sind.In a further particularly preferred embodiment, the polymeric compounds B) common that they are not used as a solid, anhydrous preparation can be, because after removal of the solvent z. B. no longer redispersible or are not stable in storage.
Die erfindungsgemäßen Präparationen können selbstverständlich auch weitere Zusatzstoffe C) enthalten. Als solche kommen beispielsweise Neutralisationsmittel, Dispergatoren, Entschäumer, Hydrophobiermittel oder Färbereihilfsmittel in Frage.The preparations according to the invention can of course also be used for other purposes Contain additives C). As such there are, for example, neutralizing agents, Dispersants, defoamers, water repellents or dyeing aids in question.
Als Neutralisationsmittel können beispielsweise Alkalisalze von aromatischen Sulfonsäuren, schwachen anorganischen Säuren bzw. Mono- oder Dicarbonsäuren verwendet werden. Bevorzugt werden die Neutralisationsmittel in einer Menge von 5 bis 20 Gew.-%, bezogen auf die feste Präparation, eingesetzt.Alkali salts of aromatic, for example, can be used as neutralizing agents Sulphonic acids, weak inorganic acids or mono- or dicarboxylic acids be used. The neutralizing agents are preferred in an amount of 5 up to 20 wt .-%, based on the solid preparation, used.
Eine ganz besonders bevorzugte Präparation enthält z. B. 30 - 65 Gew.-% an aromatischen Syntanen A) in Mischung mit 10 - 40 Gew.-% an neutralisierenden und dispergierenden Zusatzstoffen C) und 15 - 25 Gew.-% eines polymeren Nachgerbstoffes B) auf Basis von Polyasparaginsäure. Bevorzugt liegt diese Präparation als Granulat vor.A very particularly preferred preparation contains e.g. B. 30 - 65 wt .-% of aromatic Syntanen A) in a mixture with 10 - 40 wt .-% of neutralizing and dispersing additives C) and 15-25% by weight of a polymeric retanning agent B) based on polyaspartic acid. This preparation is preferably as Granules before.
Eine weitere ganz besonders bevorzugte Präparation enthält 40 - 70 Gew.-% aus einer Mischung von Salzen des dreiwertigen Chroms, aromatischen Syntanen und Harzgerbstoffen als Verbindung A), 15 - 30 Gew.-% an neutralisierenden Zusatzstoffen C) und 15 - 40 Gew.-% eines polymeren Nachgerbstoffes B) aus der Gruppe der Poly(meth)acrylate oder der Polyasparaginsäuren. Die Prozentangaben beziehen sich jeweils auf die Präparation.Another very particularly preferred preparation contains 40-70% by weight a mixture of trivalent chromium salts, aromatic syntans and Resin tannins as compound A), 15-30% by weight of neutralizing additives C) and 15-40% by weight of a polymeric retanning agent B) from the group the poly (meth) acrylates or the polyaspartic acids. Get the percentages each on the preparation.
Des weiteren bevorzugt ist eine Präparation, enthaltend 20 - 40 Gew.-% an aromatischen Syntanen, 20 - 40 Gew.-% an Harzgerbstoffen und 30 - 40 Gew.-% an neutralisierenden und dispergierenden Zusatzstoffen unter Zuhilfenahme von 10 - 25 Gew.-% eines polymeren Nachgerbstoffes B).A preparation containing 20-40% by weight of aromatic is also preferred Syntanen, 20 - 40 wt .-% of resin tanning agents and 30 - 40 wt .-% of neutralizing and dispersing additives with the help of 10 - 25 % By weight of a polymeric retanning agent B).
Die genannten Präparationen sind staubarm und rieselfähig.The preparations mentioned are low in dust and free-flowing.
Die vorliegende Erfindung betrifft ebenfalls ein Verfahren zur Herstellung der erfindungsgemäßen Präparationen, das dadurch gekennzeichnet ist, dass man zu der Verbindung A) gegebenenfalls in Mischung mit C) eine wässrige Lösung und/oder Suspension von B) gibt und gegebenenfalls noch während oder im Anschluß an die Zugabe von B) trocknet. Vorzugsweise erfolgt die Zugabe der Verbindung B) zu einer festen Form der Verbindungen A) und gegebenenfalls C). Insbesondere erfolgt die Zugabe durch Aufsprühen einer wässrigen Lösung bzw. Suspension von B) innerhalb eines Mischers. Dabei kann die erhaltene Mischung zunächst pastöse Formen annehmen. Die während bzw. im Anschluß an die Zugabe der wässrigen Lösung/Suspension von B) sich anschließende Trocknung erfolgt vorzugsweise bei 20 bis 200°C, insbesondere bei 20 bis 105°C, ganz besonders bevorzugt bei 50 bis 100°C. Ebenfalls ganz besonders bevorzugt ist das erfindungsgemäße Verfahren, sofern die Zugäbe der polymeren Verbindung B) in einer wässrigen Lösung bzw. wässrigen Suspension mit einem Feststoffanteil an B) von 5 bis 60 %, insbesondere 10 bis 50 % erfolgt.The present invention also relates to a method for producing the invention Preparations that are characterized by the fact that one can connect A) optionally in a mixture with C) an aqueous solution and / or suspension of B) and, if necessary, during or after the Adding B) dries. Compound B) is preferably added a solid form of the compounds A) and optionally C). Especially done the addition by spraying on an aqueous solution or suspension of B) within a mixer. The mixture obtained can initially have pasty shapes accept. The during or after the addition of the aqueous Solution / suspension of B) subsequent drying is preferably carried out 20 to 200 ° C, especially at 20 to 105 ° C, most preferably at 50 to 100 ° C. The method according to the invention is also very particularly preferred, if the additions of the polymeric compound B) in an aqueous solution or aqueous suspension with a solids content of B) of 5 to 60%, in particular 10 to 50% is done.
Die Erfindung betrifft weiterhin die Verwendung der erfindungsgemäßen Präparationen zum Gerben und Nachgerben von vorbehandelten Häuten oder Fellen in wässriger Flotte. Gleichzeitig ist es bevorzugt, die erfindungsgemäßen Präparationen zur Herstellung von Leder oder Pelzen dadurch zu verwenden, dass man vorgegerbte Leder oder Pelze in wässriger Flotte mit den erfindungsgemäßen Präparationen behandelt. Ebenfalls Bestandteil der Erfindung sind daher Leder oder Pelze, die hergestellt worden sind unter Verwendung der erfindungsgemäßen Präparationen als Gerb- bzw. Nachgerbstoff oder die erhältlich sind durch die erfindungsgemäße Verwendung.The invention further relates to the use of the preparations according to the invention for tanning and retanning pretreated hides or skins in water Fleet. At the same time, it is preferred to use the preparations according to the invention Manufacture leather or fur to use by pre-tanning Leather or furs in an aqueous liquor with the preparations according to the invention treated. Leather or furs that are produced are therefore also part of the invention have been using the preparations according to the invention as Tanning or retanning agents or those obtainable through the use according to the invention.
In einer bevorzugten Verwendung werden die erfindungsgemässen Leder hergestellt, indem man in einer handelsüblichen Gerbapparatur wie Gerbfass, Mixer oder Dosamat gepickelte Blösse mit 6 - 10 Gew.-% des erfindungsgemässen Produktes bei 20 bis 45°C gerbt. Während des Gerbvorganges sind keine weiteren Zugabeschritte notwendig. Das gegerbte Leder wird gewaschen und auf betriebsübliche Weise nachbehandelt, wobei Nachgerbung und Fettung entfallen oder in deutlich reduzierter Weise durchgeführt werden können.In a preferred use, the leathers according to the invention are produced by using a commercial tanning equipment such as a tanning drum, blender or Dosamat pickled pellets with 6-10% by weight of the product according to the invention Tanned 20 to 45 ° C. There are no further addition steps during the tanning process necessary. The tanned leather is washed and aftertreated in the usual manner, retanning and greasing are eliminated or significantly reduced Way can be done.
In einer weiteren bevorzugten Ausführungsform wird handelsübliches Wet-Blue auf einen pH von etwa 3.5 eingestellt und anschliessend in wässriger Flotte mit 10 - 15 Gew.-% des erfindungsgemässen Mittels nachgegerbt. Das so behandelte Leder kann betriebsüblich weiter verarbeitet werden, wobei eine anschliessende Fettung entfallen oder in deutich reduzierter Form durchgeführt werden kann.In a further preferred embodiment, commercially available wet blue is applied set a pH of about 3.5 and then in an aqueous liquor with 10-15 % By weight of the agent according to the invention retanned. The leather treated in this way can are processed further in the customary manner, with no subsequent greasing or can be carried out in a significantly reduced form.
Man erhält sowohl bei der Gerbung als auch bei der Nachgerbung mit den erfindungsgemäßen Produkten Leder, die, besonders bezüglich Weichheit und Oberflächencharakter, deutlich verbesserte Eigenschaften aufweisen gegenüber Substraten, die mit herkömmlichen Produkten behandelt wurden wie z.B. Mischungen aus Salzen des dreiwertigen Chroms mit Syntanen und Neutralisationsmitteln mit 7-16 % Gehalt an Chrom, oder Nachgerbstoff-Compounds aus 20-50 % Syntanen, 20-50 % Harzgerbstoffen und 10-50 % Neutralisationsmitteln. You get with both the tanning and the retanning Products according to the invention leather which, particularly with regard to softness and Surface character, have significantly improved properties compared to Substrates that have been treated with conventional products such as Mixtures of salts of trivalent chromium with syntans and neutralizing agents with 7-16% content of chromium, or retanning compounds 20-50% syntans, 20-50% resin tannins and 10-50% neutralizers.
Naphthalin wird mit 1.4 Mol-Äquivalenten H2SO4 bei 145°C für 2 Stunden sulfoniert. Ein Gemisch aus 1000 g der so erhaltenen Naphthalinsulfonsäuren, 800 g Bishydroxyphenylsulfon und 250 ml Formaldehyd-Lösung 37 Gew.-% wird bei 100 - 120°C für 3 Stunden kondensiert. Das erhaltene Produkt wird mit Natronlauge und Phthalsäure auf pH 3.5 und einer Säurezahl von 80 eingestellt und sprühgetrocknet. Bei Verwendung als alleiniger Gerbstoff lassen sich Schrumpftemperaturen des erhaltenen Leders von 72 - 78°C erzielen.Naphthalene is sulfonated with 1.4 molar equivalents of H 2 SO 4 at 145 ° C for 2 hours. A mixture of 1000 g of the naphthalenesulfonic acids thus obtained, 800 g of bishydroxyphenyl sulfone and 250 ml of 37% by weight formaldehyde solution is condensed at 100-120 ° C. for 3 hours. The product obtained is adjusted to pH 3.5 and an acid number of 80 with sodium hydroxide solution and phthalic acid and spray-dried. When used as the sole tanning agent, shrinking temperatures of the leather obtained of 72-78 ° C. can be achieved.
Phenol wird mit 0.88 Mol-Äquivalenten H2SO4 bei 100 - 180°C sulfoniert. Die entstandene Mischung aus Phenolsulfonsäure und Bishydroxyphenylsulfon wird mit Natronlauge neutralisiert und anschließend mit 0.44 Mol-Äquivalenten Formaldehyd, bei 100 - 120°C kondensiert. Das Rohkondensat wird mit Glutarsäure auf pH 3.7 und einer Säurezahl von 80 eingestellt und sprühgetrocknet. Bei Verwendung als alleiniger Gerbstoff lassen sich Schrumpftemperaturen des Leders von 72 - 80°C erzielen.Phenol is sulfonated with 0.88 molar equivalents of H 2 SO 4 at 100 - 180 ° C. The resulting mixture of phenolsulfonic acid and bishydroxyphenylsulfone is neutralized with sodium hydroxide solution and then condensed with 0.44 molar equivalents of formaldehyde at 100-120 ° C. The raw condensate is adjusted to pH 3.7 and an acid number of 80 with glutaric acid and spray-dried. When used as the sole tanning agent, the leather's shrinking temperatures of 72 - 80 ° C can be achieved.
Naphthalin wird mit 1.4 Mol H2SO4 3 Stunden bei 145°C sulfoniert, mit 0.66 Mol Formaldehyd 3 Stunden kondensiert, abgekühlt, mit Natronlauge und Glutarsäure auf pH 3.5 und einer Säurezahl von 50 gestellt und sprühgetrocknet. Bei Verwendung in Alleingerbung lassen sich Schrumpftemperaturen des Leders von 68 - 72°C erzielen. Naphthalene is sulfonated with 1.4 mol H 2 SO 4 at 145 ° C. for 3 hours, condensed with 0.66 mol formaldehyde for 3 hours, cooled, adjusted to pH 3.5 and an acid number of 50 with sodium hydroxide solution and glutaric acid and spray-dried. When used alone, leather shrink temperatures of 68 - 72 ° C can be achieved.
1 Mol Dicyanamid wird in Gegenwart von 0.1 Mol Natriumbisulfit und 50 Tl. Sulfitablauge mit 2 Mol Formaldehyd kondensiert. Überschüssiges Formaldehyd wird mit Ammoniak als Hexamethylentetramin gebunden. Die erhaltene Lösung wird sprühgetrocknet. Bei Verwendung in Alleingerbung lassen sich Schrumpftemperaturen von 70 - 75°C erzielen.1 mol of dicyanamide is in the presence of 0.1 mol of sodium bisulfite and 50 parts of sulfite waste liquor condensed with 2 moles of formaldehyde. Excess formaldehyde is removed Ammonia bound as hexamethylenetetramine. The solution obtained is spray dried. When used alone, shrink temperatures can be reduced achieve from 70 - 75 ° C.
Eine Lösung aus 1000 g Maleinsäureanhydrid, 800 g Diethylenglycol und 800 g
Ammoniak-Lösung (25 %) wird in 4 Stunden bei steigender Temperatur von
60 - 145°C kondensiert und anschließend flüchtige Bestandteile abdestilliert. Man
setzt 6 Stunden mit 700 g hydriertem Talgfettamin um, kühlt auf 110°C ab und versetzt
mit 170 g Ölsäure und 10 g eines siliconhaltigen Entschäumers. Das Reaktionsprodukt
wird heiss in 3 l einer 2.5 gew.-%igen Ethanolaminlösung dispergiert, mit
Natronlauge neutralisiert und mit Wasserstoffperoxid gebleicht.
(siehe DE-A 19 959 949, Komponente B2 (PAS 1)).A solution of 1000 g maleic anhydride, 800 g diethylene glycol and 800 g ammonia solution (25%) is condensed in 4 hours at an increasing temperature of 60 - 145 ° C and then volatile components are distilled off. It is reacted with 700 g of hydrogenated tallow fatty amine for 6 hours, cooled to 110 ° C. and mixed with 170 g of oleic acid and 10 g of a silicone-containing defoamer. The hot reaction product is dispersed in 3 l of a 2.5% by weight ethanolamine solution, neutralized with sodium hydroxide solution and bleached with hydrogen peroxide.
(see DE-A 19 959 949, component B 2 (PAS 1)).
Zu einer Lösung aus 600 g Maleinsäureanhydrid und 1000 g Diisobutylen in 1200 ml
Toluol wird bei 75 - 95°C innerhalb von 4 Stunden kontinuierlich 24 g AIBN (Azoisobutyronitril)
in 340 ml Toluol zugegeben. Nach 3.5 Stunden wird einmalig 35 g
Styrol zudosiert. Nach 6 Stunden Nachrühren bei 95°C gibt man eine Lösung aus
1400 g Fettalkoholgemisch (C12 - C18) in 4.4 l Toluol zu und verestert 24 Stunden bei
80°C. Unter Rühren wird mit 245 g Natronlauge in 11.8 l Wasser neutralisiert und
anschliessend unter vermindertem Druck das organische Lösungsmittel durch
azeotrope Destillation entfernt.
(EP-A 0 648 846, Beispiele A, 4.)24 g of AIBN (azoisobutyronitrile) in 340 ml of toluene are continuously added to a solution of 600 g of maleic anhydride and 1000 g of diisobutylene in 1200 ml of toluene at 75-95 ° C. in the course of 4 hours. After 3.5 hours, 35 g of styrene are metered in once. After stirring for 6 hours at 95 ° C., a solution of 1400 g of a fatty alcohol mixture (C 12 -C 18 ) in 4.4 l of toluene is added and the mixture is esterified at 80 ° C. for 24 hours. The mixture is neutralized with stirring with 245 g of sodium hydroxide solution in 11.8 l of water and the organic solvent is subsequently removed under reduced pressure by azeotropic distillation.
(EP-A 0 648 846, Examples A, 4.)
400 g Acrylsäure, 600 g Cetyl-Eicosyl-Methacrylate, 10 g Radikalstarter Azoisopentansäurenitril
und eine Lösung aus 20 g 3-Mercaptopropansäure in 165 g Wasser
werden gleichzeitig über 2 Stunden mit konstanter Fliessgeschwindigkeit bei 85°C in
900 g tert-Butanol gegeben. Anschliessend wird mit 1 g Radikalstarter Azoisopentansäurenitril
in 5 g tert-Butanol versetzt und 1 Stunde bei 85°C nachgerührt. Die
Mischung wird in 2.5 kg 10 % iger Natronlauge dispergiert und das organische
Lösungsmittel destillativ entfernt.
(EP-A 0 579 267, Beispiele Process A)400 g of acrylic acid, 600 g of cetyl-eicosyl methacrylate, 10 g of radical initiator azoisopentanoic acid nitrile and a solution of 20 g of 3-mercaptopropanoic acid in 165 g of water are simultaneously added to 900 g of tert-butanol at 85 ° C. for 2 hours at a constant flow rate. Then 1 g of azoisopentanoic acid nitrile in 5 g of tert-butanol is added and the mixture is stirred at 85 ° C. for 1 hour. The mixture is dispersed in 2.5 kg of 10% sodium hydroxide solution and the organic solvent is removed by distillation.
(EP-A 0 579 267, examples Process A)
1000 g Naphthalin wird bei 140 - 145°C mit 3 Mol-Äquivalenten H2SO4 8 Stunden sulfoniert, mit Natronlauge auf pH 7 eingestellt und die Rohproduktmischung sprühgetrocknet.1000 g of naphthalene is sulfonated at 140-145 ° C. with 3 molar equivalents of H 2 SO 4 for 8 hours, adjusted to pH 7 with sodium hydroxide solution and the crude product mixture is spray-dried.
1000 g Ditolylether werden mit 1.7 Mol-Äquivalenten H2SO4 bei 120 - 125°C 4 Stunden sulfoniert und anschließend das Gemisch von Sulfonsäuren bei 105 - 108°C mit 0.7 Äquivalenten Formaldehyd. kondensiert. Die abgekühlte Lösung des Rohkondensates wird mit Natronlauge auf pH 7 eingestellt und sprühgetrocknet. 1000 g of ditolyl ether are sulfonated with 1.7 molar equivalents of H 2 SO 4 at 120-125 ° C. for 4 hours and then the mixture of sulfonic acids at 105-108 ° C. with 0.7 equivalents of formaldehyde. condensed. The cooled solution of the raw condensate is adjusted to pH 7 with sodium hydroxide solution and spray dried.
1000 g Phenol werden mit 2 Mol-Äquivalenten H2SO4 bei 120°C 2 Stunden sulfoniert. Nach dem Abkühlen stellt man mit Ammoniak auf pH 6.5 und überführt durch Sprühtrocknung in Pulverform.1000 g of phenol are sulfonated with 2 molar equivalents of H 2 SO 4 at 120 ° C. for 2 hours. After cooling, the pH is adjusted to 6.5 with ammonia and the powder is transferred by spray drying.
35 Tl Cr2(SO4)3, 15 Tl synthetischer Gerbstoff A I, 15 Tl synthetischer Gerbstoff A IV, 20 Tl Zusatzstoff C II, 10 Tl Na2CO3 und 5 Tl NaHCO2 werden bei Raumtemperatur homogen vermischt. Anschliessend versetzt may in einer Mischagglomerationsapparatur bei 90°C mit 40 Tl polymerem Nachgerbstoff B III. Man erhält ein grünes, rieselfähiges Granulat, welches in Wasser bei Raumtemperatur rückstandsfrei löslich ist.35 parts of Cr 2 (SO 4 ) 3 , 15 parts of synthetic tanning agent AI, 15 parts of synthetic tanning agent A IV, 20 parts of additive C II, 10 parts of Na 2 CO 3 and 5 parts of NaHCO 2 are mixed homogeneously at room temperature. Then, in a mixed agglomeration apparatus at 90 ° C., 40 parts of polymeric retanning agent B III are added. A green, free-flowing granulate is obtained, which is soluble in water at room temperature without residue.
Tl bedeuten Gewichtsteile.Tl mean parts by weight.
45 Tl Cr2(SO4)3, 15 Tl synthetischer Gerbstoff A IV, 15 Tl Glutarsäure, 15 Tl NaHCO3, sowie 10 Tl MgO werden bei Raumtemperatur homogen vermischt. In einer Misschagglomerationsapperatur werden bei 60°C kontinuierlich 50 Tl Nachgerbstoff B I zugegeben. Man erhält ein grünes, rieselfähiges Granulat, welches sich in Wasser bei 40°C rückstandsfrei löst. 45 parts of Cr 2 (SO 4 ) 3 , 15 parts of synthetic tanning agent A IV, 15 parts of glutaric acid, 15 parts of NaHCO 3 and 10 parts of MgO are mixed homogeneously at room temperature. 50 parts of retanning agent BI are continuously added at 60 ° C. in a mis agglomeration apparatus. A green, free-flowing granulate is obtained, which dissolves without residue in water at 40 ° C.
20 Tl Tara, 20 Tl Mimosa, 20 Tl synthetischer Gerbstoff A I, 30 Tl Zusatzstoff C I sowie 10 Tl NaHCO3 werden bei Raumtemperatur homogen vermischt und bei 80°C mit 60 Tl polymerem Nachgerbstoff B III versetzt. Die erhaltene Paste wird heiss extrudiert. Nach dem Abkühlen erhält man ein rieselfähiges, lagerstabiles Granulat.20 parts of Tara, 20 parts of Mimosa, 20 parts of synthetic tanning agent AI, 30 parts of additive CI and 10 parts of NaHCO 3 are mixed homogeneously at room temperature and mixed with 60 parts of polymeric retanning agent B III at 80 ° C. The paste obtained is extruded hot. After cooling, a free-flowing, storage-stable granulate is obtained.
40 Tl synthetischer Gerbstoff A II, 35 Tl Zusatzstoff C II, 10 Tl Zusatzstoff C III sowie 15 Tl Na-Acetat werden in 60 Tl Wasser bei 80°C gelöst und anschliessend 100 Tl polymerer Nachgerbstoff B II zugegeben. Man trocknet durch Wirbelschicht-Sprühgranulation bei 140 bis 150°C Zulufttemperatur und erhält ein feinkörniges, rieselfähiges Granulat.40 parts of synthetic tanning agent A II, 35 parts of additive C II, 10 parts of additive C III and 15 parts of Na acetate are dissolved in 60 parts of water at 80 ° C and then 100 parts of polymeric retanning agent B II were added. It is dried by fluidized bed spray granulation at 140 to 150 ° C supply air temperature and receives a fine-grained, free-flowing granules.
50 Tl synthetischer Gerbstoff A I, 10 Tl Synthetischer Gerbstoff A IV, 30 Tl Zusatzstoff C I sowie 10 Tl NaHCO3 werden bei Raumtemperatur intensiv vermischt und durch Zugabe von 30 Tl polymerem Nachgerbstoff B III bei 80°C agglomeriert. Man erhält ein rieselfähiges Granulat, das in Wasser bei 45°C rückstandsfrei löslich ist.50 parts of synthetic tanning agent AI, 10 parts of synthetic tanning agent A IV, 30 parts of additive CI and 10 parts of NaHCO 3 are mixed intensively at room temperature and agglomerated by adding 30 parts of polymeric retanning material B III at 80 ° C. A free-flowing granulate is obtained which is soluble in water at 45 ° C. without residue.
20 Tl synthetischer Gerbstoff A I, 10 Tl synthetischer Gerbstoff A III, 20 Tl synthetischer Gerbstoff A IV, 40 Tl Zusatzstoff C II sowie 10 Tl NaHCO3 werden bei Raumtemperatur homogen vermischt. Bei 60°C werden in einer Mischagglomerationsapparatur kontinuierlich 50 Tl polymerer Gerbstoff B II zugegeben. Man erhält ein rieselfähiges, lagerstabiles Granulat, das in Wasser bei Raumtemperatur rückstandsfrei löslich ist. 20 parts of synthetic tanning agent AI, 10 parts of synthetic tanning agent A III, 20 parts of synthetic tanning agent A IV, 40 parts of additive C II and 10 parts of NaHCO 3 are mixed homogeneously at room temperature. 50 parts of polymeric tanning agent B II are continuously added at 60 ° C. in a mixed agglomeration apparatus. A free-flowing, storage-stable granulate is obtained which is soluble in water at room temperature without residue.
15 Tl synthetischer Gerbstoff A I, 15 Tl synthetischer Gerbstoff A III, 20 Tl synthetischer Gerbstoff Leukotan® SD 1000 (Polyacrylsäure, Rohm and Haas) 40 TI Zusatzstoff C II sowie 10 Tl NaHCO3 werden bei Raumtemperatur homogen vermischt und anschliessend bei 80°C 60 Tl polymerer Nachgerbstoff B II zugegeben. Die erhaltene Paste wird bei 100°C extrudiert und liefert nach Abkühlen ein rieselfähiges Granulat.15 parts of synthetic tanning agent AI, 15 parts of synthetic tanning agent A III, 20 parts of synthetic tanning agent Leukotan® SD 1000 (polyacrylic acid, Rohm and Haas) 40 parts of TI additive C II and 10 parts of NaHCO 3 are mixed homogeneously at room temperature and then at 80 ° C 60 Tl of polymeric retanning agent B II added. The paste obtained is extruded at 100 ° C. and, after cooling, provides free-flowing granules.
Haut (Rind, Spaltstärke 2.5 mm) wird auf handelsübliche Weise entkälkt, gebeizt und mit einem Pickel aus 6 % Kochsalz, 0.5 % Ameisensäure und 1.0 % Schwefelsäure auf pH 2.8 eingestellt. Bei Raumtemperatur gibt man 9 % eines Produktes gemäß Beispiel 11 zu und gerbt 2 Stunden bei Raumtemperatur. Anschließend wird die Haut über Nacht alle 60 min für 5 min bewegt und die Temperatur langsam auf 45°C angehoben. Die Flotte wird abgelassen, das Leder gewaschen, und auf betriebsübliche Weise nachgegerbt, gefärbt, gefettet und fertiggestellt.Skin (beef, split thickness 2.5 mm) is decalcified, stained and in the usual way with a pimple made of 6% table salt, 0.5% formic acid and 1.0% sulfuric acid adjusted to pH 2.8. At room temperature, 9% of a product is added Example 11 and tanned for 2 hours at room temperature. Then the skin Moved overnight every 60 min for 5 min and the temperature slowly to 45 ° C raised. The fleet is drained, the leather washed, and to normal business Retanned, dyed, greased and finished.
Das erhaltene Leder ist gegenüber handelsüblichen Vergleichsprodukten weicher und weist eine bessere Narbenfestigkeit auf, die Färbung ist egaler.The leather obtained is softer and softer than commercially available comparison products has better scar strength, the coloring is more level.
Wet Blue (Rind, Spaltstärke 1,1 mm) wird im Fass bei 35°C in 100 % Flotte mit 7 % eines Produktes gemäss Beispiel 12 für 2 Stunden bewegt. Man wäscht, fettet bei 50°C in 100 % Flotte mit 7 % eines handelsüblichen synthetischen Fettes, fixiert durch portionsweise Zugabe von 2 % Ameisensäure und stellt auf betriebsübliche Weise fertig. Wet Blue (beef, gap thickness 1.1 mm) is in the barrel at 35 ° C in 100% liquor with 7% of a product moved according to Example 12 for 2 hours. You wash, grease 50 ° C in 100% liquor with 7% of a commercially available synthetic fat, fixed by adding 2% formic acid a little at a time and switching to normal operating conditions Way done.
Wet Blue (Rind, Falzstärke 1.5 mm) wird im Faß durch Behandlung mit Oxalsäure in 200 % Flotte auf pH 3.5 eingestellt und die Flotte abgelassen. Anschließend gibt man bei 40°C 150 % Wasser sowie 12 % eines Mittels gemäß Beispiel 15 zu. Nach 60 min. wird 1 % Farbstoff zugegeben und 90 min bei 50°C gefärbt. Man fixiert durch portionsweise Zugabe von Ameisensäure, läßt die Flotte ab, wäscht und stellt daß Leder auf übliche Weise fertig.Wet blue (beef, fold thickness 1.5 mm) is in the barrel by treatment with oxalic acid in 200% liquor adjusted to pH 3.5 and the liquor drained. Then you give at 40 ° C 150% water and 12% of an agent according to Example 15. After 60 minute 1% dye is added and dyed at 50 ° C for 90 min. You fixate through portionwise addition of formic acid, drains the liquor, washes and makes that Leather finished in the usual way.
Claims (15)
- Solid preparations comprisingat least one compound A), capable of raising the shrinkage temperature of an untanned pelt by at least 10°C on treatment of the pelt with a compound A) in water at a temperature of 20-50°C,at least one different polymeric compound B) where 10 to 80% by weight of the monomer units bear one or more C2-C40-alkyl radicals and the polymer B) contains 1 to 10 mol/kg acid groups, especially carboxyl and/or carboxylate groups, and optionallyfurther additives C).
- Solid preparations according to Claim 1, characterized in that they are granular, preferably with an average particle size of 0.5 to 5 mm.
- Solid preparations according to Claim 1, characterized in that the compound A) is selected from the group consisting of mineral tanning materials, vegetable tanning materials, aromatic syntans and resin tanning materials.
- Solid preparations according to Claim 1, characterized in that their residueless water solubility or emulsifability at 20°C is more than 50 g/l.
- Solid preparations according to Claim 1, characterized in that the compound A) is a mineral tanning material, preferably a salt of trivalent chromium.
- Solid preparations according to Claim 1, characterized in that the compound A) is an aromatic syntan, especially a condensation product of naphthalenesulphonic acid, phenolsulphonic acid, bishydroxyphenyl sulphone and/or oxyditolnenesulphonic acid and formaldehyde and/or urea.
- Solid preparations according to Claim 1, characterized in that the polymeric compound B) is selected from the group consisting of polyacrylates (B1) and polyaspartic acids (B2).
- Solid preparations according to Claim 1, comprising
45 to 95% by weight of at least one compound A), 5 to 50% by weight of at least one compound B), and 0 to 50% by weight of one or more additives C). - Solid preparations according to Claim 1, characterized in that they include neutralizers, dispersants, defoamers, hydrophobicizers and/or dyeing auxiliaries as further additives C).
- Solid preparations according to Claim 9, characterized in that the neutralizers used are alkali metal salts of aromatic sulphonic acids, weak inorganic acids and/or mono- and dicarboxylic acids.
- Process for producing solid preparations according to Claim 1, characterized in that the compound A) optionally in mixture with C) is admixed with an aqueous solution and/or suspension of B) and if necessary drying is carried out during or after the addition of B).
- Use of the preparations according to Claim 1 for tanning and retanning hides or skins.
- Process for producing leathers or furs, characterized in that pretreated hides or skins are treated with an aqueous preparation according to Claim 1 in an aqueous float.
- Process for producing leathers or furs, characterized in that pretanned leather or furs are treated with a solid preparation according to Claim 1 in an aqueous float.
- Leathers or furs produced using a solid preparation according to Claim 1 or obtainable by a process according to Claims 13 or 14.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10002048A DE10002048A1 (en) | 2000-01-19 | 2000-01-19 | Tannin / retanning preparations |
DE10002048 | 2000-01-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1118682A1 EP1118682A1 (en) | 2001-07-25 |
EP1118682B1 true EP1118682B1 (en) | 2003-12-17 |
Family
ID=7627970
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP01100041A Expired - Lifetime EP1118682B1 (en) | 2000-01-19 | 2001-01-08 | Preparations of tanning/ retanning agents |
Country Status (8)
Country | Link |
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EP (1) | EP1118682B1 (en) |
CN (1) | CN1230558C (en) |
AR (1) | AR027515A1 (en) |
AT (1) | ATE256754T1 (en) |
BR (1) | BR0100104B1 (en) |
DE (2) | DE10002048A1 (en) |
ES (1) | ES2210038T3 (en) |
MX (1) | MXPA01000660A (en) |
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DE102005031043A1 (en) * | 2005-07-02 | 2007-01-25 | Lanxess Deutschland Gmbh | Polyaspartic acid derivatives in polysiloxane-containing coating compositions |
CN105586444B (en) * | 2016-01-06 | 2017-12-26 | 四川大学 | A kind of leather retanning filler prepared with phenol sulfonic acid hydrolysis tanning waste |
CN114736998B (en) * | 2022-04-12 | 2023-10-20 | 浙江通天星集团股份有限公司 | Production process of low-odor low-VOC (volatile organic compound) cow leather sofa leather |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US4526581A (en) * | 1983-02-07 | 1985-07-02 | Rohm And Haas Company | Process for producing leather |
CH676365A5 (en) * | 1988-09-28 | 1991-01-15 | Ciba Geigy Ag | |
DE4118007A1 (en) * | 1991-06-01 | 1992-12-03 | Basf Ag | CONDENSATION PRODUCTS FROM SULFONATED PHENOLS, UREA, OTHER ORGANIC NITROGEN BASES AND FORMALDEHYDES AND THEIR USE AS TANTS AND AS SPRAY AIDS FOR REDISPENSABLE POLYMER POWDER |
-
2000
- 2000-01-19 DE DE10002048A patent/DE10002048A1/en not_active Withdrawn
-
2001
- 2001-01-08 AT AT01100041T patent/ATE256754T1/en not_active IP Right Cessation
- 2001-01-08 DE DE50101155T patent/DE50101155D1/en not_active Expired - Fee Related
- 2001-01-08 ES ES01100041T patent/ES2210038T3/en not_active Expired - Lifetime
- 2001-01-08 EP EP01100041A patent/EP1118682B1/en not_active Expired - Lifetime
- 2001-01-15 AR ARP010100171A patent/AR027515A1/en active IP Right Grant
- 2001-01-18 MX MXPA01000660A patent/MXPA01000660A/en not_active Application Discontinuation
- 2001-01-18 CN CNB011016876A patent/CN1230558C/en not_active Expired - Fee Related
- 2001-01-18 BR BRPI0100104-3A patent/BR0100104B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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ATE256754T1 (en) | 2004-01-15 |
MXPA01000660A (en) | 2002-08-06 |
CN1306093A (en) | 2001-08-01 |
CN1230558C (en) | 2005-12-07 |
ES2210038T3 (en) | 2004-07-01 |
BR0100104A (en) | 2001-08-28 |
BR0100104B1 (en) | 2012-01-10 |
AR027515A1 (en) | 2003-04-02 |
DE50101155D1 (en) | 2004-01-29 |
EP1118682A1 (en) | 2001-07-25 |
DE10002048A1 (en) | 2001-07-26 |
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