EP1029930B1 - Gerbverfahren - Google Patents
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- Publication number
- EP1029930B1 EP1029930B1 EP99125142A EP99125142A EP1029930B1 EP 1029930 B1 EP1029930 B1 EP 1029930B1 EP 99125142 A EP99125142 A EP 99125142A EP 99125142 A EP99125142 A EP 99125142A EP 1029930 B1 EP1029930 B1 EP 1029930B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- tanning
- minutes
- run
- sodium bicarbonate
- 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
-
- 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
- C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes
Definitions
- a tanning process was developed in which the raw skin was pretanned with a glutardialdehyde after a usual pimple.
- This pre-tanning made it possible to subsequently mechanically treat the raw skin, e.g. B. to fold using ground knife cylinder, ie to bring it to a uniform leather thickness.
- This folding creates temperatures of up to 50 to 60 ° C.
- a raw, not pre-tanned skin burns already at temperatures of 38 - 42 ° C, so that this pre-tanning cannot be done without.
- the actual tanning was carried out with vegetable (vegetable) and / or synthetic organic tanning agents after the mechanical treatment. After tanning, the steps of greasing, dyeing, washing, drying and finishing were usually carried out in order to obtain a ready-to-use leather.
- the raw skin was in about 16 hours Tanned barrel.
- staining and greasing were again takes about 22 to 24 hours.
- the tanning barrels were definitely two nights occupied before the leather could then be dried.
- a total of about 48 hours were needed.
- No. 2,941,859 A discloses the use of glutaraldehyde as a tanning agent over a pH range known from 4.5 to 10.
- In Happich W.F. et al. (“The tanning of shears Sheepskins with glutaraldehyde "in Leder (1965), page 44) relates to tanning with gluataraldehyde the pH being adjusted to 6.5, 7.6 and 8.6.
- DE 41 02 545 A1 describes a tanning process using a dialdehyde that at a pH from 2 to 7 is carried out. From DE 39 29 366 A1 and EP 0 607 554 A1 tanning agents and tanning processes are also known.
- the object of the present invention was therefore to provide a process for tanning skins to provide, which can be done in a shorter time.
- this is achieved by a process for tanning hides, in which a skin is treated with a tanning liquor which has a dialdehyde as tanning agent, the pH of the tanning liquor being increased from 2.5 to 4.0 to 5.5 or initially more is increased and a vegetable and / or a synthetic organic tanning agent is added to the tanning fluff at a pH of 4.1 to 5.5.
- the term "skin" includes the skins of large animals, such as cattle and horses, the skins of smaller animals, such as sheep, goats and hares, which are also referred to as furs, and the skins of fish and reptiles , Birds and whales understood.
- the tanning process can also be carried out in a manner that is gentle on the hair side of the skin be performed.
- nakedness is favorably used in the method according to the invention, i. H. the untanned dermis freed from epidermis and subcutaneous connective tissue.
- the skin Before tanning, the skin can be acidified by pimples, being used as a pimple inorganic acids, such as sulfuric acid, and common salt, optionally with additives of organic acids such as formic acid can be used.
- pimple inorganic acids such as sulfuric acid, and common salt
- organic acids such as formic acid
- the pimples can be carried out, for example, as follows: To a liquor (aqueous medium, for example water), for example in an amount of about 100% by weight, based on the gap weight of the skin to be tanned, sodium chloride, e.g. B. 8 wt .-%, based on the gap weight, formic acid, for. B. 0.8 wt .-%, based on the gap weight, an 85% solution, and sulfuric acid, for. B. 0.6 wt .-%, based on the gap weight, a 96% solution added. Furthermore, a fatliquor, e.g. B.
- an alkyl sulfate derivative such as alkyl (C 12 -C 14 ) polyglycol ether (8-12EO) sulfate, and / or high molecular weight hydrocarbons, such as aromatic-free mineral oils, are added.
- the fatliquor can be used in an amount of about 1.5% by weight, based on the gap weight. After pickling, the pH of the liquor is usually 2.5 to 4.0.
- the skin to be treated can be added to such a fleet of pimples.
- the skin can but also in water and then the necessary for pimples Chemicals such as table salt, acid and optionally fatliquor can be added. All of the chemicals can be added all at once or individually in the latter case, the time between the additions of the individual chemicals can be about 5 to 20 minutes.
- the process of pimples is usually during 2 to 4 hours.
- the skin is treated with a tanning liquor which has a dialdehyde as a tanning agent.
- “Tanning liquor” means the aqueous medium used. This can include water or process water, for example.
- the amount of the tanning process liquor used can be 50% by weight to 300% by weight, based on the weight of the pimples, be.
- the quantity is given in relation to the weight of the pimple, i.e. H. that after the pimples present skin weight, it should be noted that the expert, based on this information, can also determine the corresponding quantities for other reference quantities.
- This tanning liquor has a dialdehyde as the tanning agent, the dialdehyde either first added to the tanning liquor and then to the skin to be tanned or first to Tanning liquor the skin and then the dialdehyde can be added.
- the amount of dialdehyde used can be 1.0 to 5.0% by weight, based on the Pimple weight, depending on the desired properties of the leather article.
- the dialdehyde can be in the form of a solution, e.g. B. in water, added to the tanning liquor become. For example, 20 to 60% aqueous solutions, especially 24% to 55% aqueous solutions are used. These solutions are in one such an amount added that the above amount of dialdehyde in the Tanning liquor is reached.
- the pH of the tanning liquor is from initially 2.5 to 4.0, in particular 2.5 to 3.5, to a pH of 5.5 or more, e.g. B. 5.5 to 7.0, in particular about 6.5, increased.
- the relatively acidic pH at the start of tanning is cheap to ensure a good penetration of the tanning agent into the leather interior. If this pH is not already present after the pimples, it can be adjusted by adding a Acid or a base can be adjusted accordingly.
- the increase in pH should not in one step but preferably for a period of 8 to 25 hours, in particular 20 to 25 hours, as otherwise it would be too quick to raise the pH value leads to a superficial accumulation of the tannin, causing a shrunk leather with poor tearability is obtained. It has therefore it has been shown to be beneficial to increase the pH during 8 to 25 hours make.
- the pH at the end of the process should be greater than 5.5. The higher the The final value of the pH is, the better the fullness of the leather.
- Bases can be used to increase the pH, e.g. B. sodium bicarbonate, which as Solids, liquids or as solutions, e.g. B. in water can be used.
- B. sodium bicarbonate which as Solids, liquids or as solutions, e.g. B. in water can be used.
- the pH value every 20 to 40 minutes, in particular about every 30 minutes, can be increased by 0.1 to 0.7 pH units. Then you leave the tanning barrel during run for about 12 to 18 hours and then increase, depending on the pH after Run in the manner indicated above to a pH of about 6.5. Under the term "let it run” in the sense of the present invention is understood to mean that the tanning drum moves at a speed of 6 to 18 revolutions per minute becomes.
- a base e.g. B. Sodium bicarbonate
- the tanning liquor furthermore has a modified dialdehyde.
- modified dialdehyde is understood to mean chemically modified dialdehydes of any kind which can be obtained, for example, by treating dialdehyde with molasses and / or SO 3 .
- modified dialdehydes are known in this technical field, they are referred to, for example, as “partially etherified dialdehydes” and are available under this name.
- the modified dialdehyde is used in an amount of 0 to 2% by weight, in particular 0.5 to 1.5% by weight, based on the weight of the pimple.
- modified dialdehydes achieve a particularly fashionable effect, in particular a more beautiful appearance, such as better fullness and fastness to perspiration, of the leather products.
- the modified glutardialdehydes can be used as an aqueous solution, e.g. B. in a concentration of about 45%, the tanning liquor.
- the modified dialdehyde is preferably a modified glutaraldehyde.
- An example of a modified glutardialdehyde is the commercial product "Relugan GTW" from BASF Aktiengesellschaft.
- the addition of the modified glutardialdehyde to the tanning liquor can be carried out before or during the The pH is raised.
- a vegetable and / or a synthetic one can be used for tanning in the course of increasing the pH value organic tanning agents are added to the tanning liquor.
- organic tanning agents are added to the tanning liquor.
- Upholstery leather made from animal skins usually contain surface defects, e.g. scarred wounds. These have to if necessary, be removed by grinding and embossing.
- Upholstery rugs are used during processing then drawn over edges, whereby the embossing can disappear. This is with the additional use of vegetable and / or synthetic organic tanning agents not observable.
- the skin becomes dimensionally stable so that you can grind it can.
- the synthetic and vegetable tanning agents can be used in an amount of up to 20% by weight, based on the weight of the pimples.
- Synthetic organic tannins solubilized by sulfonation Aldehyde condensation products of aromatic bases in particular of phenol, Cresol, naphthalene and naphthol can be used.
- This also includes the so-called Resin tannins, d. H. Urea or melamine-formaldehyde condensation products.
- Other Synthetic tanning agents are aldehydes, such as formaldehyde, but not those Dialdehydes are to be understood. More unsaturated fats (tears) can also be used become.
- Tannins of vegetable origin are common and come in various Plant parts. It can be tannins or tannins, protect them the plants against putrefaction. Pests or animal feed. Can be used as vegetable tannins both the condensed tannins and hydrolyzable tannins are used.
- the vegetable and / or synthetic organic tanning agents are added Conveniently not at the beginning of the tanning process, but when a pH of 4.1 to 5.5, for example 4.7 to 5.5, preferably about 5.0 is reached. The addition is made at these pH values, the effectiveness of this plant and / or synthetic tanning agents
- Preferred tanning methods are given in Tables 1 and 2 below, in which, in addition to tanning, the steps of washing, folding and greasing are also described. Production of leather from pickled nakedness, the percentages being% by weight and relating to the weight of the pick in the tanning process. operation fleet Temp.
- Base lecithin (soy or rapeseed lecithin mixed with emulsifier) z.
- B. CUTAPOL TIS-MF 3 1-10%
- CUTAPOL TIS-MF 3 1-10%
- CUTAPOL ELV 60 0 0.5-3% 85% formic acid solution 20 0 pH 4.0 0.5-3% 85% formic acid solution 30 0- pH 3.6
- the leather can be post-treated after tanning be, e.g. B. by folding, greasing, dyeing, washing, drying and dressing. in this connection these are common steps that are known to a person skilled in the art.
- the tanning process described is ideal for the production of all types of leather Type, especially soft leather types, such as clothing leather, car leather and furniture leather.
- the method according to the invention has a number of advantages. It allows the complete tanning without the use of heavy metal salts, especially Chromium salts, as a tanning agent. Furthermore, especially compared to the above Pretanning described with glutardialdehyde and tanning with vegetable or synthetic tanning agents have a shorter tanning time and a reduced need for chemicals observe. Due to the reduced tanning time it is possible to increase the capacities of the tanneries to increase. The durability of embossments of leathers obtained with these processes is excellent, especially when the combination tanning of Dialdehyde is carried out with synthetic and / or vegetable tannins.
- the leather obtainable with the tanning process described above also has a very good softness, firm grain, grindability and physical fastness, such as Tensile strength, tensile strength and puncture resistance. Furthermore, the formaldehyde content low and the fogging value and other parameters correspond to the Automotive industry requirements for leather. What the automotive industry requires There is also a fastness level with regard to light fastness and fastness to heat yellowing outstanding.
- the present invention furthermore relates to the use of a A composition comprising a dialdehyde described above and optionally a modified dialdehyde, for use in one above described tanning process.
- Tanning Liquor (water) 150% on fold weight, temperature 35 ° C 0.5 to fold weight EDTA for water softening + 0.5% on fold weight Sodium bicarbonate, run for 20 minutes, pH control (4.4) + 0.5% on fold weight
- Synthetic tanning agent (50% solution) based on hydroxyarylsulfonic acid condensates (see above) + 1.5 on folding weight
- Synthetic tanning agent based on hydroxyarylsulfonic acid condensates (see above) + 1.5 on folding weight
- Synthetic tanning agent (50% solution) based on hydroxyarylsulfonic acid condensates (see above) + 1.5 on folding weight
- Synthetic tanning agent (50% solution) based on hydroxyarylsulfonic acid condensates (see above) + 1.5 on folding weight
- Synthetic tanning agent based on hydroxyarylsulfonic acid condensates (see above) + 1.5 on folding weight
- Synthetic tanning agent based on hydroxyarylsulfonic acid condens
- Tanning process according to the invention (combination tanning with synthetic tanning agent) 1.
- Pimple as in example 2.
- Tanning Brisk 100% on pimple weight, 25 ° C
- sodium bicarbonate pH 3.5 run for 30 minutes 0.25% on pimple weight
- sodium bicarbonate pH 3.9 run for 30 minutes 0.25% on pimple weight
- sodium bicarbonate pH 4.7 run for 30 minutes 6.00% on pimple weight synthetic tanning agent hydroxyarylsulfonic acid ester condensate; see Example 1
- Tanning process according to the invention (combination tanning with vegetable tanning agent) 1.Pimples: as in example 1 2.
- Tanning Brisk 100% on picket weight, 25 ° C Addition of: 6.0% on pimple weight Glutardialdehyde, 50% solution + 1.0% on pimple weight Partly etherified glutaraldehyde (Relugan GTW from BASF AG), 45% solution, run for 120 minutes 0.25% on pimple weight
- sodium bicarbonate pH 3.5 run for 30 minutes 0.25% on pimple weight
- sodium bicarbonate pH 4.6 run for 30 minutes 0.25% on pimple weight Let sodium bicarbonate pH 5.0 run for 30 minutes 6.00% on pimple weight vegetable tannin (Mimosa, 75% active; see Example 1); Baptize for 30 minutes; pH control
- Tanning process according to the invention (combination tanning with synthetic tanning agent) 1.Pimples as in example 1 2.
- Tanning Brisk 100% on pimple weight, 25 ° C
- Glutardialdehyde (24% solution) 1.0% on pimple weight partially etherified glutardialdehyde (Relugan GTW from BASF AG) 45% solution, let run for 120 minutes 0.25% on pimple weight
- sodium bicarbonate pH 3.0 run for 30 minutes 0.25% on pimple weight Let sodium bicarbonate pH 3.2 run for 30 minutes 0.25% on pimple weight Let sodium bicarbonate pH 3.4 run for 30 minutes 0.25% on pimple weight Let sodium bicarbonate pH 3.9 run for 30 minutes 0.25% on pimple weight
- sodium bicarbonate pH 3.8 Let it run for 30 minutes 0.25% on pimple weight Let sodium bicarbonate pH 3.9 run for 30 minutes 0.25% on pimple weight Let sodium bicarbonate pH 4.1 run for 30 minutes 6.00% on pimple weight synthetic tanning agent - (hydroxyary
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Meat, Egg Or Seafood Products (AREA)
Description
Unter dem Begriff "Haut" werden Im Sinne der vorliegenden Erfindung die Häute von großen Tieren, wie Rinder und Pferde, die Häute von kleineren Tieren, wie Schafe, Ziegen und Hasen, die auch als Felle bezeichnet werden, sowie die Häute von Fischen, Reptilien, Vögeln und Walen verstanden.
Herstellung von Leder aus gepickelter Blöße, wobei die Prozentangaben Gew.-% bedeuten und bei der Gerbung auf das Pickelgewicht bezogen sind. | ||||||
Arbeitsgang | ||||||
Flotte | Temp. (°C) | Menge | Produkt | Zeit (in Minuten) | We | Bemerkung |
Gerben | 20-30 | |||||
50-300 % | Pickelflotte | 10 | 0 | Bé 6.0 | ||
2-8% | 24%ige Glutar- | |||||
dialdehydlösung | ||||||
1 - 3% | 40 % ige Lösung eines | 120 | 0 | |||
modifizierten Glutardi- | ||||||
aldehydes | ||||||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 3,5 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 3,7 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 3,9 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 4,1 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 4,3 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 4,7 | ||
0 - 15% | synthetischer Gerb- | |||||
stoff, z. B. TANNIT VWL | 90 | 0 | pH 4,4 | |||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 4,7 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 4,7 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 5,0 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 5,6 | ||
über Nacht (etwa 16 Stunden) bewegen; am Morgen bewegen | 15 | 0 | pH 5,3 | |||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 6,1 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0- | pH 6,5 | ||
Waschen | ||||||
20 - 45 | 50-300% | 5 | 0- | |||
Leder auf Bock, ausrecken, falzen auf 0,7 bis 3,0 mm Prozentangabe auf Falzgewicht | ||||||
Fettung | ||||||
20 - 45 | 50 - 300% | |||||
0,5-20% | Fischölprodukt, z. B. | |||||
Basislecithin (Soja- | ||||||
oder Raps-Lecithin | ||||||
mit Emulgator verrührt) | ||||||
z. B. CUTAPOL TIS-MF 3 | ||||||
1-10% | CUTAPOL ELV | 60 | 0 | |||
0,5-3% | 85%ige Ameisensäure- | |||||
Lösung | 20 | 0 | pH 4,0 | |||
0,5-3% | 85%ige Ameisensäure- | |||||
Lösung | 30 | 0- | pH 3,6 | |||
Waschen | ||||||
20 - 45 | 50-300% | 10 | 0- | |||
Waschen | ||||||
20 - 45 | 50-300% | 10 | 0- | |||
Leder über Nacht auf Bock | ||||||
Ausrecken, hängetrocknen, konditionieren, stollen, millen |
Herstellung von Leder aus gepickelter Blöße, wobei Prozentangaben Gew.-% bedeuten und bei der Gerbung auf das Pickelgewicht bezogen sind. | ||||||
Arbeitsgang | ||||||
Flotte | Temp. | Menge | Produkt | Zeit (in Minuten) | We | Bemerkung |
20-30 | 50-300 % | Pickelflotte | 10 | 0 | Bé 6.0 | |
2-8% | 24%ige Glutar- | |||||
dialdehydlösung | ||||||
1 - 3% | 40 % ige Lösung eines | 120 | 0 | |||
modifizierten Glutardi- | ||||||
aldehydes | ||||||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 3,5 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 3,7 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 4,0 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 4,3 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 4,6 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 5,0 | ||
0 - 20% | pflanzlicher Gerb- | |||||
stoff, z. B. Mimosa | 90 | 0 | pH 4,7 | |||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 4,7 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 5,1 | ||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 5,8 | ||
über Nacht (etwa | ||||||
16 Stunden) bewegen; am Morgen bewegen | 15 | 0 | pH 5,3 | |||
0,1-0,4% | Natriumbicarbonat | 30 | 0 | pH 6,5 | ||
Waschen | ||||||
20 - 45 | 50-300% | 5 | 0- | |||
Leder auf Bock, ausrecken, falzen auf 0,7 bis 3,0 mm Prozentangabe auf Falzgewicht | ||||||
Fettung | ||||||
20 - 45 | 50 - 300% | |||||
0,5-20% | Fischölprodukt, z. B. Basislecithin (Soja- oder Raps-Lecithin mit Emulgator verrührt) | |||||
z. B. CUTAPOL TIS-MF 3 | ||||||
1-10% | CUTAPOL ELV | 60 | 0 | |||
0,5-3% | 85%ige Ameisensäure-Lösung | 20 | 0 | pH 4,0 | ||
0,5-3% | 85%ige Ameisensäure-Lösung | 30 | 0- | pH 3,6 | ||
Waschen | ||||||
20 - 45 | 50-300% | 10 | 0- | |||
Waschen | ||||||
20 - 45 | 50-300% | 10 | 0- | |||
Leder über Nacht auf Bock | ||||||
Ausrecken, hängetrocknen, konditionieren, stollen, millen |
1.) Pickel | ||
Flotte (Wasser) 100,0 % auf Spaltgewicht, d. h. es wurde gespaltetes Leder eingesetzt; Temperatur: 25°C | ||
Zusatz von | ||
8.0% bezogen auf Spaltgewicht | NaCl, 8,0° Bé, 10 Minuten laufenlassen, (Gerbfaß rotiert mit einer Geschwindigkeit von etwa 10 bis 16 Umdrehungen pro Minute) | |
1,5% bezogen auf Spaltgewicht | Alkylsulfat-Fettungsmittel (Alkyl (C12-C14) potyglykolether (8 - 12 EO)sulfat) und hochmolekulare Kohlenwasserstoffe (aromatenfreie Mineralöle), 20 Minuten laufen lassen | |
0,8% bezogen auf Spaltgewicht | Ameisensäure (85%ige-Lösung), 15 Minuten laufen lassen | |
0,6% bezogen auf Spaltgewicht | Schwefelsäure (96%ige Lösung), 120 Minuten laufen lassen. Der pH beträgt jetzt 3,2 | |
2.) Vorgerbung | ||
1,8% auf Spaltgewicht | modifizierter Glutardialdehyd (Relugan GTW der BASF AG) (45%ige Lösung), 120 Minuten laufen lassen | |
0,1% auf Spaltgewicht | Natriumbicarbonat Faß Ober Nacht (etwa 15 bis 16 Stunden) laufen lassen, am Morgen pH mit Natriumbicarbonat auf 4 einstellen. | |
2,0% auf Spaltgewicht | synthetischer Gerbstoff (50%ige Lösung) auf Basis Hydroxyarylsulfonsäure-Kondensaten (methylenverknüpfte Hydroxyphenysulfonsäure-Kondensale, z. B. Tonnit VWL) | |
3. Abwelken (Entwässern) | ||
4. Falzen: auf 0,9 - 1,0 mm | ||
5. Gerben | ||
Flotte (Wasser) 150% auf Falzgewicht, Temperatur 35°C | ||
0,5 auf Falzgewicht | EDTA zur Wasserenthärtung | |
+ 0,5% auf Falzgewicht | Natriumbicarbonat, 20 Minuten laufen lassen, pH-Kontrolle (4,4) | |
+ 0,5% auf Falzgewicht | Synthetischer Gerbstoff (50%ige Lösung) auf Basis von Hydroxyarylsulfonsäure-Kondensaten (vgl. vorstehend) | |
+ 1.5 auf Falzgewicht | Gemisch von Sulfoesterderivaten (Fettalkohol (C12 - C16) ester aliphalischer Sulfonsäuren) und hochmolekularen Glyceriden (sulfitierte Fischöle) (Fettungsmittel) | |
+ 1,5% auf Falzgewicht | Gemisch aus Alkylphosphorsäure-esterderivaten (Alkyl (C12 - C18) polyglykolethermono/di-phosphorsäureester-Salz), 20 Minuten laufen lassen | |
6,0% auf Falzgewicht | synthetischer Gerbstoff auf Basis von Hydroxylarylsulfonsäure-Kondensaten (vgl. vorstehend) (50%ige Lösung), 20 Minuten taufen lassen | |
Flottenwechsel | ||
Neue Flotte 50% auf Falzgewicht, 35°C | ||
20,0% auf Falzgewicht | Vegetabilgerbstoff Mimosa (mit einem Gehalt von 75% an aktivem Gerbstoff), wenn es gewünscht wird, wird ein Farbstoff zugesetzt; 20 Minuten laufen lassen | |
3,0% auf Falzgewicht | Gemisch von Sulfoesterderivaten und hochmolekularen Glyceriden (Fettungsmittel) (vgl. vorstehend) | |
+ 2,0% auf Falzgewicht | Gemisch aus Alkylphosphorsäureester derivaten (vgl. vorstehend) und Pflanzen- | |
ölen (Fettungsmittel); über Nacht laufen lassen; am Morgen pH-Kontrolle, nach 10 Minuten bewegen pH 4,5 | ||
0,3% auf Falzgewicht | Ameisensäure (85%ige Lösung) ergibt pH 4,1 | |
6. Waschen | ||
Flotte 100% auf Falzgewicht, 35 °C, 10 Minuten | ||
7. Fettung | ||
Flotte 150% auf Falzgewicht, 45 °C | ||
Zusatz von | ||
10,0% auf Falzgewicht | der unter Ziff.5 genannten Fettungsmittel, 90 Minuten laufen lassen | |
0,5% auf Falzgewicht | Ameisensäure (85%ige-Lösung), 20 Minuten laufen lassen | |
0,5% auf Falzgewicht | EDTA gegen Wasserhärte, 10 Minuten laufen lassen | |
0,5% auf Falzgewicht | Ameisensäure (85%ige-Lösung) 60 Minuten laufen lassen; pH-Kontrolle 3,7 | |
8. Topffärbung | ||
Flotte 200% auf Falzgewicht, 45°C | ||
Zusatz von | ||
0,5% auf Falzgewicht | Fixiermittel (hochmolekulare Amidaldehyd-Kondensate), 20 Minuten laufen lassen; üblicher Farbstoff nach Bedarf; 20 Minuten laufen lassen | |
1,0% auf Falzgewicht | Ameisensäure (85%ige Lösung); pH | |
Kontrolle: 3,3 | ||
1,0% auf Falzgewicht | Fixiermittel (wie oben), 60 Minuten laufen lassen | |
9. Waschen: | ||
Flotte 200% auf Falzgewicht, 20°C, 10 Minuten danach Trocknen und Zurichten |
1. Pickel: wie in Beispiel | ||
2. Gerben | ||
Flotte 100% auf Pickelgewicht, 25°C | ||
Zusatz von: | ||
6,0% auf Pickelgewicht Glutardialdehyd (50%ige Lösung) | ||
+ | 1,0% auf Pickelgewicht | teilveretherter Glutardialdehyd (Relugan GTW der BASF AG); 45%ige Lösung, 120 Minuten laufen lassen |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 3,5 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 3,7 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 3,9 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 4,1 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 4,3 30 Minuten laufen lassen | |
0,25% auf Pickeigewicht | Natriumbicarbonat pH 4,7 30 Minuten laufen lassen | |
6,00% auf Pickelgewicht | synthetischer Gerbstoff (Hydroxyarylsulfonsäureester-Kondensat; vgl. Beispiel 1), 50%ige Lösung 90 Minuten laufen lassen, pH-Kontrolle 4,4 | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 4,7 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 4,7 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 5,0 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 5,6 30 Minuten laufen lassen, über Nacht (etwa 16 Stunden) bewegen, am Morgen bewegen, 15 Minuten; pH-Kontrolle 5,3 | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 6,2 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 6,5 30 Minuten laufen lassen | |
3. Waschen: Flotte 300% auf Pickelgewicht, 40°C, 5 Minuten | ||
4. Abwelken: | ||
5. Falzen: auf 0,9 - 1,0 mm | ||
6. Fetten: wie in Beispiel 1 | ||
7.Waschen: Flotte 300% auf Pickelgewicht, 20°C, 10 Minuten | ||
8. Topffärbung: wie in Beispiel 1 | ||
9. Waschen: Flotte 300%, 20°C, 10 Minuten | ||
Trocknen, Zurichten |
1. Pickeln: wie in Beispiel 1 | ||
2. Gerben: | ||
Flotte 100% auf Picketgewicht, 25°C | ||
Zusatz von: | ||
6,0% auf Pickelgewicht | Glutardialdehyd, 50%ige Lösung | |
+ 1,0% auf Pickelgewicht | teilveretherter Glutardialdehyd (Relugan GTW der BASF AG), 45% ige Lösung, 120 Minuten laufen lassen | |
0.25% auf Pickelgewicht | Natriumbicarbonat pH 3,5 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 3,7 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 4,0 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 4,3 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 4,6 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 5,0 30 Minuten laufen lassen | |
6,00% auf Pickelgewicht | vegetabilischer Gerbstoff (Mimosa, 75% aktiv; vgl. Bsp. 1); 30 Minuten taufen lassen; pH-Kontrolle: 4,7 | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 4,7 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 5,1 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 5,8 30 Minuten laufen lassen über Nacht (etwa 16 Stunden) bewegen, am Morgen bewegen, 15 Minuten; pH-Kontrolle 5,3 | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 6,5 30 Minuten laufen lassen | |
3. Waschen: Flotte 300% auf Pickelgewicht, 40°C, 5 Minuten | ||
4. Abwelken: | ||
5. Falzen: auf 0,9 - 1,0 mm | ||
6. Fetten: wie in Beispiel 1 | ||
7.Waschen: Flotte 300% auf Pickelgewicht, 20°C, 10 Minuten | ||
8. Topffärbung: wie in Beipiel 1 | ||
9. Waschen: Flotte 300%, 20°C, 10 Minuten | ||
Trocknen, Zurichten |
1. Pickeln wie in Beispiel 1 | ||
2. Gerben: | ||
Flotte 100% auf Pickelgewicht, 25°C | ||
Zusatz von: | ||
6,0% auf Pickelgewicht | Glutardialdehyd (24%ige Lösung) | |
1,0% auf Pickelgewicht | teilveretherter Glutardialdehyd (Relugan GTW der BASF AG) 45%ige Lösung, 120 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 3,0 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 3,2 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH.3,4 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 3,9 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 3,8 | |
30 Minuten laufen lassen | ||
0,25% auf Pickelgewicht | Natriumbicarbonat pH 3,9 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 4,1 30 Minuten laufen lassen | |
6,00% auf Pickelgewicht | synthetischer Gerbstoff -(Hydroxyarylsulfonsäureester-Kondensat; vgl. Bsp. 1); 50%ige Lösung, pH 4.0; 90 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 4,1 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 4,3 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 4,7 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 5,0 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 5,3 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 5,9 30 Minuten laufen lassen | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 5,9 30 Minuten laufen lassen Über Nacht bewegen, am Morgen bewegen (15 Minuten) pH 5,9 | |
0,25% auf Pickelgewicht | Natriumbicarbonat pH 6,5 30 Minuten laufen lassen | |
3. Waschen: Flotte 300% auf Pickelgewicht, 40°C, | ||
4. Abwelken: | ||
5. Falzen: auf 1,2 mm | ||
6. Waschen: Flotte 300% auf Pickelgewicht, 30°C | ||
7. Topffärbung: wie in Beispiel 1 |
Claims (6)
- Verfahren zum Gerben von Häuten, bei dem eine Haut mit einer Gerbflotte behandelt wird, die einen Dialdehyd als Gerbstoff aufweist, wobei der pH-Wert der Gerbflotte von anfänglich 2,5 bis 4,0 auf 5,5 oder mehr erhöht und der Gerbflotte ein pflanzlicher und/oder ein synthetischer organischer Gerbstoff bei einem pH-Wert von 4,1 bis 5,5 zugegeben wird.
- Verfahren nach Anspruch 1, bei dem der Dialdehyd Glutardialdehyd ist.
- Verfahren nach Anspruch 1 oder 2, bei dem der pH-Wert während 8 bis 25 Stunden erhöht wird.
- Verfahren nach einem der Ansprüche 1 bis 3, bei dem die Gerbflotte weiterhin einen modifizierten Dialdehyd enthält.
- Verfahren nach einem der Ansprüche 1 bis 4, wobei das Verfahren ein Einbadverfahren ist.
- Verwendung einer Zusammensetzung, umfassend einen Dialdehyd und gegebenenfalls einen modifizierten Dialdehyd, in einem Verfahren nach einem der Ansprüche 1 bis 5.
Applications Claiming Priority (2)
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DE19906190A DE19906190A1 (de) | 1999-02-15 | 1999-02-15 | Gerbverfahren |
DE19906190 | 1999-02-15 |
Publications (2)
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EP1029930A1 EP1029930A1 (de) | 2000-08-23 |
EP1029930B1 true EP1029930B1 (de) | 2003-11-05 |
Family
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EP99125142A Expired - Lifetime EP1029930B1 (de) | 1999-02-15 | 1999-12-16 | Gerbverfahren |
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EP (1) | EP1029930B1 (de) |
AT (1) | ATE253648T1 (de) |
DE (2) | DE19906190A1 (de) |
Families Citing this family (7)
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CN1333084C (zh) * | 2006-02-20 | 2007-08-22 | 陕西科技大学 | 一种预防皮革中六价铬的助剂及其制备方法 |
CN1333085C (zh) * | 2006-02-20 | 2007-08-22 | 陕西科技大学 | 六价铬含量达标皮革的生产方法 |
CN103695575B (zh) * | 2013-12-25 | 2015-05-27 | 宁夏吴忠市精艺裘皮制品有限公司 | 一种山羊皮合成鞣剂鞣制工艺 |
CN104818355B (zh) * | 2015-04-17 | 2016-10-26 | 四川大学 | 一种含铬皮革复鞣填充剂及其制备方法 |
CN104946822A (zh) * | 2015-06-05 | 2015-09-30 | 四川大学 | 一种应用酸性蛋白酶协同提高皮革柔软度的方法 |
ITUB20152180A1 (it) * | 2015-07-14 | 2017-01-14 | Db Patents Ltd | Metodo migliorato per conciare una pelle animale. |
IT201700095318A1 (it) * | 2017-08-23 | 2019-02-23 | Db Patents Ltd | Metodo per conciare una pelle animale. |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2971814A (en) * | 1957-12-23 | 1961-02-14 | Seligsberger Ludwig | Tanning with alkaline glyoxal |
US2941859A (en) * | 1959-04-08 | 1960-06-21 | Martin L Fein | Tanning with glutaraldehyde |
DE2215948C3 (de) * | 1972-04-01 | 1975-10-16 | Basf Ag, 6700 Ludwigshafen | Wäßrige Gerbstoff-Formulierungen und Verfahren zum Gerben, Vor- oder Nachgerben mit den Formulierungen |
HU206395B (en) * | 1988-09-09 | 1992-10-28 | Simontornyai Boergyar | Process for producing chrome-free soft leather |
DE4102545A1 (de) * | 1991-01-29 | 1992-07-30 | Basf Ag | Verfahren zum alleingerben, vorgerben und mitgerben von bloessen und fellbloessen und zum nachgerben von leder und fell |
DE4242076A1 (de) * | 1992-12-14 | 1994-06-16 | Roehm Gmbh | Gerbmittel und Gerbverfahren |
DE4335192A1 (de) * | 1993-10-15 | 1995-04-20 | Basf Ag | Glyoxalmono (alpha- oder beta-formylalkyl)acetale als Gerbmittel bei der Leder- und Pelzherstellung |
-
1999
- 1999-02-15 DE DE19906190A patent/DE19906190A1/de not_active Withdrawn
- 1999-12-16 EP EP99125142A patent/EP1029930B1/de not_active Expired - Lifetime
- 1999-12-16 DE DE59907620T patent/DE59907620D1/de not_active Expired - Fee Related
- 1999-12-16 AT AT99125142T patent/ATE253648T1/de not_active IP Right Cessation
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DE19906190A1 (de) | 2000-08-17 |
EP1029930A1 (de) | 2000-08-23 |
ATE253648T1 (de) | 2003-11-15 |
DE59907620D1 (de) | 2003-12-11 |
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