EP0184741B1 - Method of greasing leather and skins - Google Patents

Description

und nachfolgende Alkylierung durch Umsetzung mit Acrylsäure oder Methacrylsäure oder deren Ester.The invention relates to a process for greasing leather and furs, characterized in that an amphoteric surfactant is used as the greasing agent, which is prepared by condensation of C ₆ -C ₂₂ fatty acids or corresponding fatty acid esters with aminoalkylalkanolamines of the general formula

and subsequent alkylation by reaction with acrylic acid or methacrylic acid or their esters.

The preparation of such amphoteric surfactants is described, for example, in DE-OS 3018201 (EP-A 0 040 346). They are then prepared by condensation of Cε-C22 fatty acids with the aminoalkylalkanolamines of the general formula given in a molar ratio of 1: 1 to 1: 1.5 and subsequent alkylation with vinylogenic compounds, the alkylation products optionally quaternizing depending on the structure and extent of the reaction May have nitrogen atoms. Since the condensation products of fatty acid and aminoalkylalkanolamine generally contain a more or less high proportion of diamide, an alkaline pretreatment is preferably carried out before the alkylation, the diamide being converted into the monoamide. In the subsequent alkylation, this leads to improved amphoteric surfactants with, in particular, increased storage stability.

For the preparation of the amphoteric surfactants to be used according to the invention, preference is given to using saturated or unsaturated C ₁₂ -C ₂₂ fatty acids or corresponding fatty acid esters. These can be present as pure components or preferably as mixtures of natural or synthetic origin. Examples of this are mixtures of coconut fatty acid, tallow fatty acid, trans-fatty acid, rapeseed oil fatty acid, and corresponding methyl esters or triglycerides. The amine component is preferably aminoethylethanolamine. The reaction is preferably carried out in a molar ratio of fatty acid or fatty acid residue: aminoalkylalkanolamine, such as 1: 1 to 1: 1.5. The alkylation is carried out using acrylic acid or methacrylic acid and their esters, such as methyl acrylate or methyl methacrylate. In the latter case, the amphoteric surfactants are formed by subsequent saponification of the alkylation products with aqueous sodium hydroxide solution.

The amphoteric surfactants described have high emulsion resistance to the hardness constituents of water and to alkali salts. In the case of leather and fur greasing with good greasing of the leather, they result in a pleasantly soft, slimy and supple handle. Colorings are very brilliant with good levelness. Suede leather has a silky fiber with a nice writing effect.

The amphoteric surfactants can be used alone or in combination with conventional leather greasing agents based on sulfated, sulfited or sulfochlorinated oils or fats as well as in combination with anionic and / or nonionic emulsifiers, such as alkylbenzenesulfonates, fatty alcohol sulfates, fatty alcohol ethosulfates, fatty acid alkanolamide ethosulfates, fatty alcohol ethylenesulfates, and fatty alcohol sulfosulfinates, sulfosulfinate adducts, sulfosuccinate adducts, and sulfosuccinate adducts be used. The proportion of amphoteric surfactants can be 10-100% by weight, based on the fatty substance. Because of the amphoteric character of the claimed products, combinations with cationic fatliquoring agents or emulsifiers, such as e.g. Dimethyldistearylammonium chloride possible. The amphoteric surfactants are leather and fur greasing agents which can be used without problems. They are used in the customary manner in the form of aqueous emulsions in an amount of 3-15% by weight of active substance, based on the shaved weight of the leather.

Examples A. Preparation of various amphoteric surfactants 1. Base of tallow fatty acid

2117.0 g (8.0 mol) of tallow fatty acid were in the presence of 3 g of 50% hypophosphorous acid (for color stabilization) with 915 g (8.8 mol) of aminoethylethanolamine in a three-necked flask equipped with a stirrer, thermometer, nitrogen purge and distillation attachment , reacted with slow heating to 200 ° C; at approx. 151 ° C the water split off. After stirring for 1 hour at 200 ° C. under normal pressure and for a further hour at 20 mbar, the residue obtained: 2626 g of aminoamide (tallow-like, yellowish mass of the amine number 144).

To produce the amphoteric surfactant, 97.2 g (0.25 mol) of the aminoamide were mixed in a three-necked flask with stirring and a thermometer at 90 ° C. with 4 g of 50% sodium hydroxide solution and 25 g of water and for 1 hour at 90-95 ° C. stirred to destroy diamide. Then 316.6 g of water and 18.0 g (0.25 mol) of acrylic acid were added and the mixture was stirred at 85 ° C. for 5 hours. A finely divided dispersion with 25% active substance was obtained.

2. Basis beet oil fatty acid, rich in eruca (55% erucic acid)

2191 g (7.0 mol) of beet oil fatty acid, rich in eruca, 800.8 g (7.7 mol) of aminoethylethanolamine and 3.0 g of 50% hypophosphorous acid were converted to the aminoamide as indicated under 1.

Yield: 2635 g of a viscous, brown oil, amine number 124.

To prepare the amphoteric surfactant, 862.5 g (1.9 mol) of the aminoamide, 30.5 g of 50% sodium hydroxide solution, 2969.5 g of water and 137.5 g (1.91 mol) of acrylic acid were added in the order given below 1 specified, implemented. Here too, a finely dispersed product with 25% active substance was obtained.

3. Base beet oil, low erucic acid (2% erucic acid)

1109 g (1.25 mol) of beet oil, low erucic acid, and 391 g (3.75 mol) of aminoethylethanolamine were placed in a three-necked flask equipped with a stirrer, thermometer, nitrogen purge and distillation head in the presence of 22.5 g of 30% sodium methylate solution Heated to 180 ° C for 3 hours, then stirred at 180 ° C for 3 hours. The crude reaction product (aminoamide) was a brownish oil, amine number 142.

To prepare the amphoteric surfactant, 847 g (2.14 mol) of the aminoamide were dispersed in 2000 g of water and reacted with 153 g (2.13 mol) of acrylic acid by stirring at 80-90 ° C. for 8 hours. The product obtained was a viscous brown liquid with 33% active substance.

4. Base trans fatty acid

2014 g (7 mol) of trans fatty acid (J.Z. 117), 800.8 g (7.7 mol) of aminoethylethanolamine and 3.0 g of hypophosphorous acid were converted to the aminoamide as indicated under 1.

Yield: 2450 g of brown oil, amine number 155.

To prepare the amphoteric surfactant, 1267 g (3.5 mol) of the aminoamide, 252 g (3.5 mol) of acrylic acid and 4500 g of water were reacted. A viscous brown liquid with 25% active substance was obtained.

5. Based on coconut oil fatty acid

• a) Zur Herstellung des Amphotensids wurden 311,8 g (1 Mol) des Aminoamids, 16,2 g 50%ige Natronlauge, 599,0 g Wasser und 72,0 g (1 Mol) Acrylsäure in der angegebenen Reihenfolge wie unter 1 angegeben, umgesetzt. Das erhaltene Produkt war eine viskose, klare Flüssigkeit mit ca. 40% Aktivsubstanz.
• b) Eine weitere Umsetzung wurde wie unter a) angegeben durchgeführt, jedoch wurden statt 72,0 g Acrylsäure 86 g (1 Mol) Acrylsäuremethylester eingesetzt. Nach 4stündigem Rühren bei 70 °C wurde nicht umgesetzter Acrylsäuremethylester im Vakuum abgezogen und das rohe Umsetzungsprodukt durch Zugabe von 40 g NaOH und 650 ml Wasser durch 4stündiges Erwärmen auf 80 °C verseift. Es wurde eine viskose, klare Flüssigkeit mit ca. 40% Aktivsubstanz erhalten.

412.0 g (2.0 mol) of coconut oil fatty acid were in the presence of 0.5 ml of 50% hypophosphorous acid with 228.8 g (2.2 mol) of aminoethylethanolamine in a three-necked flask equipped with a stirrer, thermometer, nitrogen purge and distillation head brought to slow reaction to about 200 ° C to react. After stirring for 1 hour at 200 ° C., 46.5 ml of water of reaction had separated out. The mixture was stirred for a further hour at about 20 mbar, further water of reaction and excess amine being distilled off (a total of 47 g). 540.5 g of a pale yellow oil which slowly solidified at room temperature, amine number 180, remained as a residue.

• a) To prepare the amphoteric surfactant, 311.8 g (1 mol) of the aminoamide, 16.2 g of 50% sodium hydroxide solution, 599.0 g of water and 72.0 g (1 mol) of acrylic acid were in the order given as indicated under 1 , implemented. The product obtained was a viscous, clear liquid with about 40% active substance.
• b) A further reaction was carried out as indicated under a), but instead of 72.0 g of acrylic acid, 86 g (1 mol) of methyl acrylate were used. After stirring for 4 hours at 70 ° C., unreacted methyl acrylate was removed in vacuo and the crude reaction product was saponified by adding 40 g of NaOH and 650 ml of water by heating to 80 ° C. for 4 hours. A viscous, clear liquid with about 40% active substance was obtained.

B. Examples of use

• Waschen: 200 % Wasser 40 °C 10 min neue Flotte
  • 100 % Wasser 40 °C
  • 1 % Na-Formiat ₄₀ min
  • 1 % Na-Bicarbonat Spülen 50 °C
• Nachger- 100 % Wasser 50 °C
• bung: 4 % Phenolkondensa- 30 min tionsprodukt
  • ₀,_5% Ammoniak
  • 3 % Farbstoff 30 min
  • 3 % Produkt Beispiel 5a
  • 3 % sulfatiertes Esteröl 40 min
  • 2 % sulfitiertes Esteröl
  • 3 % Acrylatgerbstoff 30 min
  • 0,5% Ameisensäure 15 min

6. Manufacture of sheep's clothing leather Material: wet-blue% by weight on fold weight

• Wash: 200% water 40 ° C 10 min new liquor
  • 100% water 40 ° C
  • 1% Na formate ₄₀ min
  • 1% Na bicarbonate rinse at 50 ° C
• Afterwards 100% water 50 ° C
• Exercise: 4% phenol condensation product
  • _{0.5 %} ammonia
  • 3% dye 30 min
  • 3% product example 5a
  • 3% sulfated ester oil 40 min
  • 2% sulfited ester oil
  • 3% acrylic tanning agent 30 min
  • 0.5% formic acid 15 min

Soft leather with a full, round handle. Uniform, floral coloring

• 50 Teile Produkt Beispiel 3
• 50 Teile sulfitiertes Esteröl
• 1:1 bis 1:2 mit Wasser emulgieren und mit der Bürste auftragen.
• Weiche, mollige, leichte Pelze.

7. Spread lubrication of rabbit fur

• 50 parts of product example 3
• 50 parts of sulfited ester oil
• Emulsify 1: 1 to 1: 2 with water and apply with a brush.
• Soft, plump, light furs.

• Gew.-% auf Falzgewicht
• Waschen: 200 % Wasser 45 °C 10 min neue Flotte
• Nachger- 100 % Wasser 45 °C
• bung: 2 % Chromsulfat 33% bas.
• 2 % Phenolkondensa- 45 min tionsprodukt
• 1 % Na-Aluminiumsilicat Spülen 40 °C
• Neutrali- 100 % Wasser 40 °C
• sation 2 % Na-Bicarbonat 60 min neue Flotte
• Färbung 100 % Wasser 50 °C
• und 2 % Naphthalinkonden- 15 min Fettung: sationsprodukt
• _{1 %} Ammoniak
• 3 % Farbstoff 45 min 2 % Produkt Beispiel 5a
• 5 % FS sulfatierte
• Esteröle 45 min 4 % FS sulfatierte Esteröle
• 1 % FS Sulfosuccinat
• 1,5% Ameisensäure 15min
• 1,5% Ameisensäure 30 min
• Es werden tuchweiche, mollige, leicht schmalzige Möbelleder erhalten.

8. Manufacture of furniture leather Material: wet-blue

• % By weight on fold weight
• Wash: 200% water 45 ° C 10 min new liquor
• Afterwards 100% water 45 ° C
• exercise: 2% chromium sulfate 33% bas.
• 2% phenol condensation product
• 1% Na aluminum silicate rinse 40 ° C
• Neutral 100% water 40 ° C
• tion 2% Na bicarbonate 60 min new liquor
• Coloring 100% water 50 ° C
• and 2% naphthalene condensate - 15 min lubrication: product
• _1% ammonia
• 3% dye 45 min 2% product example 5a
• 5% FS sulfated
• Ester oils 45 min 4% FS sulfated ester oils
• 1% FS sulfosuccinate
• 1.5% formic acid 15min
• 1.5% formic acid 30 min
• Cloth-soft, chubby, slightly slimy furniture leather is obtained.

• Gew.-% auf Trockengewicht
• Broschie- 0,5% FAS
• ren: 1 % Ammoniak 2 Std neue Flotte
• Färbung: 300 % Wasser 60 °C
• 2 % Phenolkondensationsprodukt 60 min
• 1 % Ammoniak
• 7 % Farbstoff
• 2 % Ameisensäure 15min
• 2 % Ameisensäure 30 min
• 1 % Produkt Beispiel 3
• 1,5% kat. Fettungsmittel 30 min gut waschen

9. Production of cow suede material: crust leather

• % By weight on dry weight
• Brochure 0.5% FAS
• Ren: 1% ammonia 2 hours new fleet
• Coloring: 300% water 60 ° C
• 2% phenol condensation product 60 min
• 1% ammonia
• 7% dye
• 2% formic acid 15min
• 2% formic acid 30 min
• 1% product example 3
• 1.5% cat. Wash fatliquor well for 30 minutes

A silky velor fiber with a brilliant color and a beautiful writing effect is obtained.

• Gew.-% auf Falzgewicht
• Waschen: 200 % Wasser 40 °C 10 min neue Flotte
• Neutrali- 100 % Wasser 40 °C
• sation: 0,5% Na-Formiat 15min
• 0,5% Na-Aluminiumsilicat 30 min
• Waschen: 100 % Wasser 60 °C 10 min neue Flotte
• Nachger- 100 % Wasser 60 °C
• bung: 2 % amphoteres Färbe- 15 min reihilfsmittel
• 1 % Farbstoff 15 min
• 2 % Acrylatgerbstoff 15 min
• 3 % Phenolkondensationsprodukt 30 min
• 2 % Produkt Beispiel 1
• ₃ % sulfatiertes Fischöl ₄₅ min
• 2 % Chlorparaffinsulfonat
• 0,5% Ameisensäure 15 min

10. Manufacture of cowhide leather Material: wet-blue

• % By weight on fold weight
• Wash: 200% water 40 ° C 10 min new liquor
• Neutral 100% water 40 ° C
• sation: 0.5% Na formate 15 min
• 0.5% Na aluminum silicate 30 min
• Wash: 100% water 60 ° C 10 min new liquor
• Afterwards 100% water 60 ° C
• exercise: 2% amphoteric stain- 15 min
• 1% dye 15 min
• 2% acrylic tanning agent 15 min
• 3% phenol condensation product 30 min
• 2% product example 1
• ₃ % sulfated fish oil ₄₅ min
• 2% chloroparaffin sulfonate
• 0.5% formic acid 15 min

The leather is very soft (softyl leather) with good fullness, uniform, brilliant aniline coloring.

Claims (5)

1. A process for fat liquoring leather and skins, characterized in that the fat liquoring agent used is an amphoteric surfactant produced by condensation of C₆-C₂₂ fatty acids or corresponding fatty acid esters with aminoalkyl alkanolamines corresponding to the following general formula

in which

and subsequent alkylation by reaction with acrylic acid or methacrylic acid or esters thereof.

2. A process as claimed in Claim 1, characterized in that the amphoteric surfactant used is produced by condensation of saturated or unsaturated C₁₂-C₂₂ fatty acids or corresponding fatty acid esters with aminoalkyl alkanolamine in a molar ratio of fatty acid or fatty acid residue to aminoalkyl alkanolamine of from 1:1 to 1:1,5 and subsequent alkylation with acrylic acid or methacrylic acid or esters thereof, optionally followed by hydrolysis.

3. A process as claimed in Claims 1 and 2, characterized in that the condensation product of fatty acid and aminoalkyl alkanolamine is subjected before alkylation to an alkaline pre-treatment at temperatures in the range from 70 to 100 °C.

4. A process as claimed in Claims 1 to 3, characterized in that the amphoteric surfactants are used in the form of aqueous emulsions in a quantity of from 3 to 15% by weight of active substance, based on the pared weight of the leather or skins, in the fat liquoring bath.

5. A process as claimed in Claims 1 to 4, characterized in that the amphoteric surfactants are used in combination with standard fat liquoring agents based on sulfated, sulfited or sulfochlorinated oils or fats, optionally in conjunction with anionic and/or nonionic, or cationic emulsifiers.