EP0213480A2 - Method of water-proofing leather and furs - Google Patents
Method of water-proofing leather and furs Download PDFInfo
- Publication number
- EP0213480A2 EP0213480A2 EP86111130A EP86111130A EP0213480A2 EP 0213480 A2 EP0213480 A2 EP 0213480A2 EP 86111130 A EP86111130 A EP 86111130A EP 86111130 A EP86111130 A EP 86111130A EP 0213480 A2 EP0213480 A2 EP 0213480A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- leather
- silicone oil
- furs
- carbon atoms
- 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.)
- Granted
Links
- 239000010985 leather Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000004078 waterproofing Methods 0.000 title claims abstract description 13
- 229920002545 silicone oil Polymers 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 150000001413 amino acids Chemical class 0.000 claims abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 239000008346 aqueous phase Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000839 emulsion Substances 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 8
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 8
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 238000003756 stirring Methods 0.000 description 24
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 15
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 13
- -1 polysiloxanes Polymers 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 239000012188 paraffin wax Substances 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 8
- DIOYAVUHUXAUPX-KHPPLWFESA-N Oleoyl sarcosine Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CC(O)=O DIOYAVUHUXAUPX-KHPPLWFESA-N 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- RJYOKYDKKOFLBT-UHFFFAOYSA-N 2-[methyl(octadecanoyl)amino]acetic acid Chemical compound CCCCCCCCCCCCCCCCCC(=O)N(C)CC(O)=O RJYOKYDKKOFLBT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BACYUWVYYTXETD-UHFFFAOYSA-N N-Lauroylsarcosine Chemical compound CCCCCCCCCCCC(=O)N(C)CC(O)=O BACYUWVYYTXETD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 description 2
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 2
- 239000011696 chromium(III) sulphate Substances 0.000 description 2
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- QJAUKMLCDVOYNX-UHFFFAOYSA-N formaldehyde;2-hydroxybenzenesulfonic acid Chemical compound O=C.OC1=CC=CC=C1S(O)(=O)=O QJAUKMLCDVOYNX-UHFFFAOYSA-N 0.000 description 2
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 108700004121 sarkosyl Proteins 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RVHKREBFDOJEOT-UHFFFAOYSA-N 2-[methyl(7-methyloctanoyl)amino]acetic acid Chemical compound CC(C)CCCCCC(=O)N(C)CC(O)=O RVHKREBFDOJEOT-UHFFFAOYSA-N 0.000 description 1
- DIOYAVUHUXAUPX-ZHACJKMWSA-N 2-[methyl-[(e)-octadec-9-enoyl]amino]acetic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)N(C)CC(O)=O DIOYAVUHUXAUPX-ZHACJKMWSA-N 0.000 description 1
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001887 acacia decurrens willd. var. dealbata absolute Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000004569 hydrophobicizing agent Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
Definitions
- the invention relates to a process for waterproofing leather and furs with a silicone oil and the salt of an N- (C9-C20-acyl) amino acid as an emulsifier for the silicone oil, which is carried out in the aqueous phase during or after retanning, and the use of salts of N- (C9-C20-acyl) amino acids for emulsifying silicone oil in the aqueous phase in the waterproofing of leather and furs and the mixtures used.
- a wide variety of methods for waterproofing are known for leather and furs.
- silicone oils are also used for this finishing stage.
- the polysiloxanes used are always dissolved in organic solvents such as gasoline or chlorinated hydrocarbons. Disadvantages when working with these solvents are the harmful and polluting effects as well as the fire risk when using gasoline.
- the hydrophobization with the help of organic solvents also means an additional work step and thus a considerably increased effort.
- N-acylamino acids especially fatty acid sarcosides, e.g. N-oleoyl sarcosine, in the form of their salts, are known as emulsifiers for paraffins and waxes, which can also be used, for example, in the waterproofing of leather.
- emulsifiers for paraffins and waxes which can also be used, for example, in the waterproofing of leather.
- the effects that can be achieved with waxes and paraffins are not always sufficient for today's high requirements and are usually supplemented by a separate post-hydrophobic treatment with, for example, fluorochemicals or silicone oils that are applied from the organic phase.
- the object of the invention is to develop a process for hydrophobizing leather and furs, in which organic solvents are not necessary and can be rendered hydrophobic with a silicone oil in the aqueous phase, the technical application effect on leather and furs being at least equivalent to that of silicone oils from organic Solvents should be.
- the solution to the problem consists in a process for waterproofing leather and furs, in which a silicone oil with the salt of an N- (C9-C20-acyl) amino acid as an emulsifier in an aqueous liquor onto the leather or furs to be finished during or after of retanning.
- the invention is based on the observation that N- (C9-C20-acyl) amino acids, in particular fatty acid sarcosides, in the form of their salts are excellent emulsifiers for silicone oils, so that the use in water repellent treatment of leather and furs in aqueous liquors can be demonstrated for the first time .
- Sufficiently stable aqueous emulsions of silicone oils can only be achieved with the indicated emulsifier without additional aids for the purposes of use. This was all the more surprising since the emulsifiers to be used according to the invention can also be absorbed onto the leather during use, so that one could have expected the emulsion to be destabilized.
- the invention also relates to the use of amino acids with 2 to 6 carbon atoms and with the acyl residue of a saturated or unsaturated fatty acid with 9 to 20 carbon atoms on the amine nitrogen atom, which may optionally be substituted by methyl, in the form of an alkali metal, Ammonium or alkanolamine salt for emulsifying silicone oil in the aqueous phase in the waterproofing of leather and furs during or after retanning.
- the invention thus also relates to the use of the aqueous emulsion a) or of the anhydrous mixture b) of the above-mentioned composition in aqueous liquors for hydrophobicizing leather or furs during or after retanning in an amount of from 0.5 to 20% by weight on the fold weight of the leather or wet weight of the furs.
- the particular advantage of the process according to the invention is that, in a simple procedure while avoiding organic solvents, an emulsifier for the silicone oil has been found which emulsifies the silicone oil sufficiently so that the silicone oil can penetrate the leather, followed by the addition of acid and optionally one polyvalent metal salt, the N-acylamino acid salt used is rendered ineffective as an emulsifier, so that the full hydrophobizing effect of the silicone oil comes into play. It should be emphasized that the use of organic solvents and additional auxiliaries, for example nonionic emulsifiers, can be avoided.
- Suitable silicone oils are the commercially available silicone oils with viscosities of 30 to 1,000 mPa ⁇ s, preferably 80 to 500 mPa ⁇ s. Such silicone oils can be readily used by those skilled in the art, for example Römpps Chemie-Lexikon, 7th edition, Stuttgart, 1975, pp. 3223ff, or Ullmanns Enzyklopadie der techn. Chemie, 4th ed., 1982, volume 21, pp. 512ff.
- silicone oils are suitable in which the remaining valences of silicon are saturated by hydrocarbon radicals, in particular methyl, but also ethyl, propyl or phenyl.
- silicone oils which in their hydrocarbon radicals carry organofunctional groups such as amino, mercapto or carboxyl groups. Because of these functional groups, they are easier to emulsify and thus better bind to the leather fibers.
- organofunctional groups such as amino, mercapto or carboxyl groups. Because of these functional groups, they are easier to emulsify and thus better bind to the leather fibers.
- the viscosities given are a practical measure of the molecular weights, which can often only be determined with great effort.
- Preferred silicone oils are dimethylpolysiloxanes with a viscosity of 80 to 110 mPa ⁇ s, phenylmethyl polysiloxanes with a viscosity of 85 to 120 mPa ⁇ s, dimethylpolysiloxanes with amino groups as reactive groups, characterized by an amine number of about 0.8 to 1.0 and a viscosity of 30 to 50 mPa ⁇ s, and dimethylpolysiloxanes with carboxyl groups as reactive groups, on average with 2 to 10 carboxyl groups per molecule.
- Dimethylpolysiloxanes the methyl groups of which are partly replaced by mercaptopropyl (-CH2-CH2-CH2-SH) or aminopropyl groups (-CH2-CH2-NH2) as reactive groups, are very particularly preferred. As a rule, 1 to 5%, preferably approx. 3%, of the methyl groups in the chain are replaced by these reactive substituents. It is commercially available dimethylpolysiloxanes with terminal -Si (CH3) 3 groups, which can be characterized by a viscosity range from 130 to 200, preferably 145 to 180 mPa ⁇ s. The preferred and particularly preferred silicone oils are commercially available products.
- N- (C9-C20-acyl) amino acids with 2 to 6 C atoms are those with 2 to 4 C atoms, with the amino group in the ⁇ -position to the carboxyl group and which are additionally substituted on the amine nitrogen atom by a methyl group, prefers.
- the fatty acid sarcosides of saturated or unsaturated fatty acids with 9 to 20, preferably 16 to 18, carbon atoms have a particularly superior effect.
- Suitable salts are the alkali metal salts, in particular sodium or potassium, the ammonium salts or salts of a mono-, di- or trialkanolamine having 2 to 4 carbon atoms in the alkanol radical, in particular mono-, di- or triethanolamine.
- the particularly preferred sarcoside is oleic acid sarcoside or N-oleoyl sarcosine (medialanic acid). Furthermore, the N-stearoyl sarcosine, N-lauroyl sarcosine and N-isononanoyl sarcosine are to be emphasized, in each case in the form of the salts mentioned above.
- the silicone oil and the salt of N-acylamino acid are advantageously in the form of an aqueous emulsion as a concentrate, consisting of 15 to 90% by weight of an above-mentioned silicone oil, 5 to 30% by weight of an above-mentioned salt of an N- (C9-C20- Acyl) amino acid and at least 5 to the rest of 100% by weight of water, a pH of 5 to 12, preferably 7 to 10, having been set using an alkali metal hydroxide, ammonia or an alkanolamine.
- the preferred concentrate contains 30 to 60% by weight of silicone oil, 5 to 30% by weight of salt of an N- (C9-C20-acyl) amino acid and 65 to 10% by weight of water, the pH being within a very preferred range has been set from 7.5 to 8.5.
- anhydrous concentrate consisting of 70 to 90% by weight of silicone oil and 10 to 30% by weight of one of the N-acylamino acids defined above in the form of a mono-, di- or trialkanolamine salt is used.
- the silicone oil in the aqueous phase is automatically emulsified by the salt used.
- aqueous emulsion defined above is preferred as the concentrate to be used.
- hydrophobization according to the invention can be combined with a known hydrophobizing agent, for example based on a paraffin or wax emulsion, i.e. at the same time or following a hydrophobization which is customary in aqueous liquors. A significant improvement in the water repellency effects is achieved.
- the concentrates described above can, based on the total weight of the mixture, additionally 5 to 45, preferably 10 to 30,% by weight of solid and / or liquid paraffin, for example paraffin with a melting point of 20 to 100 ° C., paraffin oil or white oil, one contain natural fats or oils, such as fish oil or bone oil, or a synthetic or natural wax, such as polyethylene waxes, polyisobutylene waxes, beeswax or carnauba wax, the weight ratio of silicone oil to paraffin expediently not exceeding the value of 1: 1.
- Solid paraffin with a melting point between 40 and 60 ° C. and white oil are particularly preferred for such a combination.
- the specified amounts of paraffin, fats, oils or waxes are easily absorbed by the concentrates.
- an above-mentioned concentrate based on the shaved weight of the leather or wet weight of the furs, in an amount of 0.5 to 20% by weight, preferably 2 to 10% by weight, optionally together with dyes, during or after the retanning. % used.
- the concentrate used is expediently diluted with water in a ratio of 1: 2 to 1: 5 and added to the working liquor.
- the hydrophobization according to the invention can also be carried out in two stages during and after retanning.
- Useful tanning agents for retanning are vegetable tanning agents and synthetic tanning agents, for example based on phenolsulfonic acid-formaldehyde condensates.
- Suitable dyes which can be used simultaneously are, for example, the customary acidic, substantive or basic aniline dyes.
- the actual hydrophobization according to the invention during or after retanning is carried out by milling in a suitable device usual way: ie with fleet lengths of 50 to 2,000%, preferably 100 to 400%, based on the fold weight of the leather or wet weight of the furs, temperatures of 20 to 60 ° C, preferably 35 to 50 ° C, with the pH at the beginning -Values are generally between 4.5 and 8.0, preferably 4.8 to 5.5.
- the hydrophobization is completed in a time between 20 to 240, preferably 30 to 120 minutes.
- the emulsifier is fixed with acid, preferably formic acid, by adjusting a pH of 3.0 to 5.0, preferably 3.8 to 4.0.
- the effect of the hydrophobization can be enhanced by an aftertreatment with a tetravalent, normal or tetravalent metal salt, in particular with a basic chromium sulfate, with aluminum sulfate, zirconium, titanium sulfate, calcium chloride or magnesium sulfate.
- salts mentioned 0.5 to 5% by weight, preferably 1 to 2% by weight, is expediently used, based on the shaved weight of the leather or wet weight of the furs.
- specified salts basic chromium sulfate and aluminum sulfate are preferred.
- Parts are parts by weight, percentages relate to the weight, unless stated otherwise.
- Example 1 160 parts of the dimethylpolysiloxane characterized in Example 1 and 40 parts of N-oleyl sarcosine (oleic acid sarcoside) are mixed with stirring and heated to 60 ° C. Then a mixture of 160 parts of water and 17.5 parts of triethanolamine heated to 60 ° C. is slowly added with stirring. The mixture is allowed to cool with stirring.
- N-oleyl sarcosine oleic acid sarcoside
- silicone oil emulsions 50.0 parts of a commercially available polysiloxane to be used according to the invention are mixed with 10.0 parts of N-oleoyl-sarcosine with stirring and heated to 60.degree. Then a mixture of 36 parts of water and 4 parts of 25% aqueous sodium hydroxide solution heated to 60 ° C. is slowly added with stirring. The complete conversion to the sodium salt is achieved by stirring until the pH is constant. The pH of the mixture is then adjusted to 7.8 to 8.0 and cooled to room temperature with stirring.
- Example 8 The commercially available polysiloxane used in Example 8 was a dimethylpolysiloxane with a viscosity of approximately 95 mPa ⁇ s, in Example 9 a phenylmethyl polysiloxane with a viscosity of approximately 95 mPa ⁇ s, in Example 10 an amino-functional dimethylpolysiloxane with an amine number of approximately 0.8 to 1.0 and a viscosity of 30 to 50 mPa ⁇ s and in Example 11 a dimethylpolysiloxane with 4 carboxyl groups in the molecule.
- Chromium pre-tanned cowhide with a fold thickness of 2.2 mm which has been deacidified to a pH value of 5.0 to 6.0, based on the fold weight, with 5% by weight of commercially available mimosa extract and 3% by weight of a commercially available synthetic tanning agent based on phenolsulfonic acid-formaldehyde condensate, 1% by weight of a commercially available aniline dye and 5% by weight of the silicone oil emulsion specified in Example 1, drummed for 1.5 hours in a tanning drum at 40 ° C., the pH of the treatment liquor being 100% 5. Is 2 to 5.5.
- Example 1 In the fresh bath of 100% water and 40 ° C., a further 3% by weight, based on the shaved weight, of the silicone emulsion specified in Example 1 is rolled into the leather within 30 minutes. It is acidified with 85% formic acid to a pH of 3.8 to 4.0 and with 2% by weight of a commercially available chrome tanning agent (Cr2O3 content of 25% and a basicity of 33%) for 90 minutes at 40 ° C fixed. The leathers are then washed, mechanically stretched and dried.
- chrome tanning agent Cr2O3 content of 25% and a basicity of 33
- chrome tanning agent chromium oxide content approx. 25%, basicity approx. 33%). After washing out, the usual drying takes place.
- Chromium-tanned cowhide (wet blue) is used for post-tanning after deacidification to pH 5.0 to 6.0, each based on the shaved weight of the leather, 7.5% by weight of a mixture of vegetable and synthetic commercial tannins based on naphthalenesulfonic acid-formaldehyde -Condensate, 1.5% by weight of a commercially available aniline dye and 7% by weight of a customary water repellent for leather based on a paraffin emulsion, drummed for 60 minutes in the drum and then for a further 30 minutes with 3% by weight of the silicone oil emulsion according to Example 1 in the drum tumbled. With further walking for 30 minutes, the mixture is acidified to a pH of 4.0 with formic acid and fixed with 1.5% by weight of commercially available chromium tanning agent within 90 minutes.
- the leather is rinsed and dried as usual.
- the wetblue leathers deacidified to a pH of 5.0 to 6.0 with commercially available deacidifying agents are retanned, dyed, as indicated in Example A, and with, based on the shaved weight, 8% by weight of a commercially available, non- Fat-repellent mixture with a hydrophobic effect, greased, acidified to a pH of 4.0 and rinsed.
- the mixture is then drummed in fresh liquor (100%, 40 ° C.) for 30 minutes with 4% by weight of the silicone oil emulsion described in Example 3 with paraffin and white oil and fixed with 1.5% by weight of commercially available chrome tanning agent for 60 minutes.
- the chrome-tanned leather deacidified to a pH of 5.0 to 6.0, is retanned with 7% by weight of a mixture of commercially available vegetable and synthetic tanning agents based on phenol condensate, based in each case on the shaved weight of the leather 1.2% by weight of aniline dye and greased with 5% by weight of commercially available, non-hydrophobic grease licker for 40 minutes.
- the mixture is then drummed with a mixture of 3% by weight of the silicone oil emulsion specified in Example 1 and 3% by weight of a commercially available hydrophobicizing agent based on paraffin emulsion, acidified to pH 3.8 to 4.0, for 30 minutes and with 5 wt.% Of a commercially available aluminum salt (Al2SO4) 3 ⁇ 18 H2O fixed for 60 min, washed out and stretched and dried as usual.
- Al2SO4 aluminum salt
Landscapes
- 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)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zum Hydrophobieren von Leder und Pelzen mit einem Siliconöl und dem Salz einer N-(C9-C20-Acyl)-aminosäure als Emulgator für das Siliconöl, das in wäßriger Phase während oder nach der Nachgerbung durchgeführt wird, sowie die Verwendung von Salzen von N-Acyl-aminosäuren als Emulgator von Siliconölen bei der Hydrophobierung von Leder und Pelzen in wäßriger Phase und die dabei verwendeten Gemische.The invention relates to a process for waterproofing leather and furs with a silicone oil and the salt of an N- (C9-C20-acyl) amino acid as an emulsifier for the silicone oil, which is carried out in the aqueous phase during or after retanning, and the use of salts of N-acylamino acids as emulsifiers of silicone oils in the waterproofing of leather and furs in the aqueous phase and the mixtures used.
Description
Die Erfindung betrifft ein Verfahren zum Hydrophobieren von Leder und Pelzen mit einem Siliconöl und dem Salz einer N-(C₉-C₂₀-Acyl)-aminosäure als Emulgator für das Siliconöl, das in wäßriger Phase während oder nach der Nachgerbung durchgeführt wird, sowie die Verwendung von Salzen von N-(C₉-C₂₀-Acyl)-aminosäuren zum Emulgieren von Siliconöl in wäßriger Phase bei der Hydrophobierung von Leder und Pelzen und die dabei verwendeten Gemische.The invention relates to a process for waterproofing leather and furs with a silicone oil and the salt of an N- (C₉-C₂₀-acyl) amino acid as an emulsifier for the silicone oil, which is carried out in the aqueous phase during or after retanning, and the use of salts of N- (C₉-C₂₀-acyl) amino acids for emulsifying silicone oil in the aqueous phase in the waterproofing of leather and furs and the mixtures used.
Für Leder und Pelze sind die verschiedensten Verfahren zum Hydrophobieren bekannt. Beispielsweise werden für diese Veredelungsstufe auch Siliconöle verwendet. Die verwendeten Polysiloxane werden dabei stets in organischen Lösungsmitteln gelöst, wie Benzin oder chlorierte Kohlenwasserstoffe, zur Anwendung gebracht. Nachteilig beim Arbeiten mit diesen Lösungsmitteln sind die gesundheitsschädlichen und umweltverschmutzenden Wirkungen sowie die Brandgefahr bei der Verwendung von Benzin. Die Hydrophobierung mit Hilfe von organischen Lösungsmitteln bedeutet auch einen zusätzlichen Arbeitsgang und damit einen wesentlich vermehrten Aufwand.A wide variety of methods for waterproofing are known for leather and furs. For example, silicone oils are also used for this finishing stage. The polysiloxanes used are always dissolved in organic solvents such as gasoline or chlorinated hydrocarbons. Disadvantages when working with these solvents are the harmful and polluting effects as well as the fire risk when using gasoline. The hydrophobization with the help of organic solvents also means an additional work step and thus a considerably increased effort.
N-Acylaminosäuren, insbesondere Fettsäuresarkoside, z.B. N-Oleoyl-sarkosin, sind in Form ihrer Salze bekannt als Emulgatoren für Paraffine und Wachse, die beispielsweise auch bei der Hydrophobierung von Leder verwendet werden können. Die mit Wachsen und Paraffinen erreichbaren Effekte reichen für die heutigen hohen Anforderungen nicht immer aus und werden in der Regel ergänzt durch eine gesonderte Nachhydrophobierung mit beispielsweise Fluorchemikalien oder Siliconölen, die aus organischer Phase aufgebracht werden.N-acylamino acids, especially fatty acid sarcosides, e.g. N-oleoyl sarcosine, in the form of their salts, are known as emulsifiers for paraffins and waxes, which can also be used, for example, in the waterproofing of leather. The effects that can be achieved with waxes and paraffins are not always sufficient for today's high requirements and are usually supplemented by a separate post-hydrophobic treatment with, for example, fluorochemicals or silicone oils that are applied from the organic phase.
Aufgabe der Erfindung ist es, ein Verfahren zum Hydrophobieren von Leder und Pelzen zu entwickeln, bei dem organische Lösungsmittel nicht notwendig und eine Hydrophobierung mit einem Siliconöl in wäßriger Phase erfolgen kann, wobei der anwendungstechnische Effekt auf Leder und Pelze wenigstens gleichwertig dem von Siliconölen aus organischen Lösungsmitteln sein soll.The object of the invention is to develop a process for hydrophobizing leather and furs, in which organic solvents are not necessary and can be rendered hydrophobic with a silicone oil in the aqueous phase, the technical application effect on leather and furs being at least equivalent to that of silicone oils from organic Solvents should be.
Die Lösung der Aufgabe besteht in einem Verfahren zum Hydrophobieren von Leder und Pelzen, bei dem man ein Siliconöl mit dem Salz einer N-(C₉-C₂₀-Acyl)-aminosäure als Emulgator in wäßriger Flotte auf die zu veredelnden Leder oder Pelze während oder nach der Nachgerbung einwirken läßt.The solution to the problem consists in a process for waterproofing leather and furs, in which a silicone oil with the salt of an N- (C₉-C₂₀-acyl) amino acid as an emulsifier in an aqueous liquor onto the leather or furs to be finished during or after of retanning.
Der Erfindung liegt die Beobachtung zugrunde, daß N-(C₉-C₂₀-Acyl)-aminosäuren, insbesondere Fettsäuresarkoside, in Form ihrer Salze hervorragende Emulgatoren für Siliconöle darstellen, so daß erstmals die Anwendung beim Hydrophobieren von Leder und Pelzen in wäßriger Flotte aufgezeigt werden kann. Dabei werden für die Anwendungszwecke genügend beständige wäßrige Emulsionen von Siliconölen nur mit dem aufgezeigten Emulgator ohne zusätzliche weitere Hilfsmittel erreicht. Dies war umso überraschender, als die erfindungsgemäß zu verwendenden Emulgatoren während der Anwendung auf das Leder mit aufziehen können, so daß man eine Destabilisierung der Emulsion hätte erwarten können.The invention is based on the observation that N- (C₉-C₂₀-acyl) amino acids, in particular fatty acid sarcosides, in the form of their salts are excellent emulsifiers for silicone oils, so that the use in water repellent treatment of leather and furs in aqueous liquors can be demonstrated for the first time . Sufficiently stable aqueous emulsions of silicone oils can only be achieved with the indicated emulsifier without additional aids for the purposes of use. This was all the more surprising since the emulsifiers to be used according to the invention can also be absorbed onto the leather during use, so that one could have expected the emulsion to be destabilized.
Gegenstand der Erfindung ist ein Verfahren zum Hydrophobieren von Leder und Pelzen mit einem Siliconöl in Gegenwart eines Salzes einer N-(C₉-C₂₀-Acyl)-aminosäure als Emulgator, das dadurch gekennzeichnet ist, daß man
- a) die wäßrige Emulsion eines Siliconöls, bestehend aus 15 bis 90 Gew.% Siliconöl, 5 bis 30 Gew.% eines Salzes einer Aminosäure mit 2 bis 6 C-Atomen und mit dem Acylrest einer gesättigten oder ungesättigten Fettsäure mit 9 bis 20 C-Atomen am Aminstickstoffatom, das gegebenenfalls zusätzlich durch Methyl substituiert sein kann, und wenigstens 5 bis Rest zu 100 Gew.% Wasser, die mit einem Alkalihydroxid, Ammoniak oder einem Alkanolamin auf einen pH-Wert von 5 bis 12, vorzugsweise 7 bis 10, eingestellt ist, oder
- b) das wasserfreie Gemisch aus 70 bis 90 Gew.% eines Siliconöls und 10 bis 30 Gew.% eines Alkanolaminsalzes einer Aminosäure mit 2 bis 6 C-Atomen und mit dem Acylrest einer gesättigten oder ungesättigten Fettsäure mit 9 bis 20 C-Atomen am Aminstickstoffatom, das gegebenenfalls zusätzlich durch Methyl substituiert sein kann,
- a) the aqueous emulsion of a silicone oil consisting of 15 to 90% by weight of silicone oil, 5 to 30% by weight of a salt of an amino acid with 2 to 6 carbon atoms and with the acyl residue of a saturated or unsaturated fatty acid with 9 to 20 carbon atoms Atoms on the amine nitrogen atom, which may optionally be additionally substituted by methyl, and at least 5 to the rest of 100% by weight of water, which are adjusted to a pH of 5 to 12, preferably 7 to 10, using an alkali metal hydroxide, ammonia or an alkanolamine is, or
- b) the anhydrous mixture of 70 to 90% by weight of a silicone oil and 10 to 30% by weight of an alkanolamine salt of an amino acid with 2 to 6 C atoms and with the acyl residue of a saturated or unsaturated fatty acid with 9 to 20 C atoms on the amine nitrogen atom which may optionally be additionally substituted by methyl,
Gegenstand der Erfindung ist auch die Verwendung von Aminosäuren mit 2 bis 6 C-Atomen und mit dem Acylrest einer gesättigten oder ungesättigten Fettsäure mit 9 bis 20 C-Atomen am Aminstickstoffatom, das gegebenenfalls zusätzlich durch Methyl substituiert sein kann, in Form eines Alkali-, Ammonium- oder Alkanolaminsalzes zum Emulgieren von Siliconöl in wäßriger Phase bei der Hydrophobierung von Leder und Pelzen während oder nach der Nachgerbung.The invention also relates to the use of amino acids with 2 to 6 carbon atoms and with the acyl residue of a saturated or unsaturated fatty acid with 9 to 20 carbon atoms on the amine nitrogen atom, which may optionally be substituted by methyl, in the form of an alkali metal, Ammonium or alkanolamine salt for emulsifying silicone oil in the aqueous phase in the waterproofing of leather and furs during or after retanning.
Die Erfindung betrifft somit auch die Verwendung der wäßrigen Emulsion a) oder des wasserfreien Gemisches b) der oben angegebenen Zusammensetzung in wäßrigen Flotten zum Hydrophobieren von Leder oder Pelzen während oder nach der Nachgerbung in einer Menge von 0,5 bis 20 Gew.%, bezogen auf das Falzgewicht des Leders oder Naßgewicht der Pelze.The invention thus also relates to the use of the aqueous emulsion a) or of the anhydrous mixture b) of the above-mentioned composition in aqueous liquors for hydrophobicizing leather or furs during or after retanning in an amount of from 0.5 to 20% by weight on the fold weight of the leather or wet weight of the furs.
Der besondere Vorteil des erfindungsgemäßen Verfahrens liegt darin, daß in einer einfachen Verfahrensweise unter Vermeidung organischer Lösungsmittel ein Emulgator für das Siliconöl gefunden wurde, der das Siliconöl ausreichend emulgiert, so daß das Siliconöl das Leder durchdringen kann, wobei anschließend durch Zugabe von Säure und gegebenenfalls eines mehrwertigen Metallsalzes das verwendete N-Acylaminosäuresalz als Emulgator unwirksam gemacht wird, so daß die volle hydrophobierende Wirkung des Siliconöls zum Tragen kommt. Betont sei, daß die Mitverwendung von organischen Lösungsmitteln und zusätzlichen Hilfsmitteln, beispielsweise nichtionischen Emulgatoren, vermieden werden können.The particular advantage of the process according to the invention is that, in a simple procedure while avoiding organic solvents, an emulsifier for the silicone oil has been found which emulsifies the silicone oil sufficiently so that the silicone oil can penetrate the leather, followed by the addition of acid and optionally one polyvalent metal salt, the N-acylamino acid salt used is rendered ineffective as an emulsifier, so that the full hydrophobizing effect of the silicone oil comes into play. It should be emphasized that the use of organic solvents and additional auxiliaries, for example nonionic emulsifiers, can be avoided.
Als Siliconöle kommen die handelsüblichen Siliconöle mit Viskositäten von 30 bis 1.000 mPa·s, bevorzugt 80 bis 500 mPa·s, in Betracht. Solche Siliconöle kann der Fachmann ohne weiteres beispielsweise Römpps Chemie-Lexikon, 7. Aufl., Stuttgart, 1975, S. 3223ff, oder Ullmanns Enzyklopädie der techn. Chemie, 4. Aufl., 1982, Band 21, S. 512ff, entnehmen. Geeignet sind beispielsweise Siliconöle, bei denen die restlichen Valenzen des Siliciums durch Kohlenwasserstoffreste, insbesondere Methyl, aber auch Ethyl, Propyl oder Phenyl, abgesättigt sind. Ganz besonders bevorzugt sind solche Siliconöle, die in ihren Kohlenwasserstoffresten teilweise organofunktionelle Gruppen, wie Amino-, Mercapto- oder Carboxylgruppen, tragen. Aufgrund dieser funktionellen Gruppen lassen sie sich leichter emulgieren und dadurch besser an die Lederfasern binden. Die angegebenen Viskositäten sind dabei ein praktisches Maß für die Molekulargewichte, die häufig nur mit großem Aufwand bestimmt werden können.Suitable silicone oils are the commercially available silicone oils with viscosities of 30 to 1,000 mPa · s, preferably 80 to 500 mPa · s. Such silicone oils can be readily used by those skilled in the art, for example Römpps Chemie-Lexikon, 7th edition, Stuttgart, 1975, pp. 3223ff, or Ullmanns Enzyklopadie der techn. Chemie, 4th ed., 1982, volume 21, pp. 512ff. For example, silicone oils are suitable in which the remaining valences of silicon are saturated by hydrocarbon radicals, in particular methyl, but also ethyl, propyl or phenyl. Very particular preference is given to those silicone oils which in their hydrocarbon radicals carry organofunctional groups such as amino, mercapto or carboxyl groups. Because of these functional groups, they are easier to emulsify and thus better bind to the leather fibers. The viscosities given are a practical measure of the molecular weights, which can often only be determined with great effort.
Bevorzugte Siliconöle sind Dimethylpolysiloxane mit einer Viskosität von 80 bis 110 mPa·s, Phenylmethyl-Polysiloxane mit einer Viskosität von 85 bis 120 mPa·s, Dimethylpolysiloxane mit Aminogruppen als reaktive Gruppen, charakterisiert durch eine Aminzahl von etwa 0,8 bis 1,0 und einer Viskosität von 30 bis 50 mPa·s, sowie Dimethylpolysiloxane mit Carboxylgruppen als reaktive Gruppen und zwar im Durchschnitt mit 2 bis 10 Carboxylgruppen pro Molekül.Preferred silicone oils are dimethylpolysiloxanes with a viscosity of 80 to 110 mPa · s, phenylmethyl polysiloxanes with a viscosity of 85 to 120 mPa · s, dimethylpolysiloxanes with amino groups as reactive groups, characterized by an amine number of about 0.8 to 1.0 and a viscosity of 30 to 50 mPa · s, and dimethylpolysiloxanes with carboxyl groups as reactive groups, on average with 2 to 10 carboxyl groups per molecule.
Ganz besonders bevorzugt sind Dimethylpolysiloxane, deren Methylgruppen teilweise durch Mercaptopropyl- (-CH₂-CH₂-CH₂-SH) oder Aminopropylgruppen (-CH₂-CH₂-CH₂-NH₂) als reaktive Gruppen ersetzt sind. In der Regel sind 1 bis 5 %, bevorzugt ca. 3 %, der Methylgruppen in der Kette durch diese reaktiven Substituenten ersetzt. Es handelt sich um handelsübliche Dimethylpolysiloxane mit endständigen -Si(CH₃)₃-Gruppen, die durch einen Viskositätsbereich von 130 bis 200, bevorzugt 145 bis 180 mPa·s, charakterisiert werden können. Die bevorzugten und besonders bevorzugten Siliconöle sind handelsübliche Produkte.Dimethylpolysiloxanes, the methyl groups of which are partly replaced by mercaptopropyl (-CH₂-CH₂-CH₂-SH) or aminopropyl groups (-CH₂-CH₂-CH₂-NH₂) as reactive groups, are very particularly preferred. As a rule, 1 to 5%, preferably approx. 3%, of the methyl groups in the chain are replaced by these reactive substituents. It is commercially available dimethylpolysiloxanes with terminal -Si (CH₃) ₃ groups, which can be characterized by a viscosity range from 130 to 200, preferably 145 to 180 mPa · s. The preferred and particularly preferred silicone oils are commercially available products.
Von den N-(C₉-C₂₀-Acyl)-aminosäuren mit 2 bis 6 C-Atomen sind solche mit 2 bis 4 C-Atomen, mit der Aminogruppe in α-Stellung zur Carboxylgruppe und die am Aminstickstoffatom zusätzlich durch eine Methylgruppe substituiert sind, bevorzugt. Davon weisen eine besondere überlegene Wirkung die Fettsäuresarkoside von gesättigten oder ungesättigten Fettsäuren mit 9 bis 20, bevorzugt 16 bis 18, C-Atomen auf.Of the N- (C₉-C₂₀-acyl) amino acids with 2 to 6 C atoms are those with 2 to 4 C atoms, with the amino group in the α-position to the carboxyl group and which are additionally substituted on the amine nitrogen atom by a methyl group, prefers. Of these, the fatty acid sarcosides of saturated or unsaturated fatty acids with 9 to 20, preferably 16 to 18, carbon atoms have a particularly superior effect.
Als Salze kommen die Alkalisalze, insbesondere des Natriums oder Kaliums, die Ammoniumsalze oder Salze eines Mono-, Di- oder Trialkanolamins mit 2 bis 4 C-Atomen im Alkanolrest, insbesondere des Mono-, Di- oder Triethanolamins, in Betracht.Suitable salts are the alkali metal salts, in particular sodium or potassium, the ammonium salts or salts of a mono-, di- or trialkanolamine having 2 to 4 carbon atoms in the alkanol radical, in particular mono-, di- or triethanolamine.
Das besonders bevorzugte Sarkosid ist das Ölsäuresarkosid oder N-Oleoyl-sarkosin (Medialansäure). Weiterhin sind insbesondere das N-Stearoyl-sarkosin, N-Lauroyl-sarkosin und N-Isononanoyl-sarkosin hervorzuheben, jeweils in Form der obengenannten Salze.The particularly preferred sarcoside is oleic acid sarcoside or N-oleoyl sarcosine (medialanic acid). Furthermore, the N-stearoyl sarcosine, N-lauroyl sarcosine and N-isononanoyl sarcosine are to be emphasized, in each case in the form of the salts mentioned above.
Das Siliconöl und das Salz der N-Acylaminosäure werden vorteilhaft in Form einer wäßrigen Emulsion als Konzentrat, bestehend aus 15 bis 90 Gew.% eines oben bezeichneten Siliconöls, 5 bis 30 Gew.% eines oben bezeichneten Salzes einer N-(C₉-C₂₀-Acyl)-aminosäure und wenigstens 5 bis Rest zu 100 Gew.% Wasser, wobei mit einem Alkalihydroxid, Ammoniak oder einem Alkanolamin ein pH-Wert von 5 bis 12, vorzugsweise 7 bis 10 eingestellt worden ist, angewandt. Das bevorzugte Konzentrat enthält 30 bis 60 Gew.% Siliconöl, 5 bis 30 Gew.% Salz einer N-(C₉-C₂₀-Acyl)-aminosäure und 65 bis 10 Gew.% Wasser, wobei der pH-Wert auf einen ganz bevorzugten Bereich von 7,5 bis 8,5 eingestellt worden ist.The silicone oil and the salt of N-acylamino acid are advantageously in the form of an aqueous emulsion as a concentrate, consisting of 15 to 90% by weight of an above-mentioned silicone oil, 5 to 30% by weight of an above-mentioned salt of an N- (C₉-C₂₀- Acyl) amino acid and at least 5 to the rest of 100% by weight of water, a pH of 5 to 12, preferably 7 to 10, having been set using an alkali metal hydroxide, ammonia or an alkanolamine. The preferred concentrate contains 30 to 60% by weight of silicone oil, 5 to 30% by weight of salt of an N- (C₉-C₂₀-acyl) amino acid and 65 to 10% by weight of water, the pH being within a very preferred range has been set from 7.5 to 8.5.
In einer weiteren Ausführungsform wird ein wasserfreies Konzentrat, bestehend aus 70 bis 90 Gew.% Siliconöl und 10 bis 30 Gew.% einer der oben definierten N-Acyl-aminosäuren in Form eines Mono-, Di- oder Trialkanolaminsalzes, verwendet.In a further embodiment, an anhydrous concentrate consisting of 70 to 90% by weight of silicone oil and 10 to 30% by weight of one of the N-acylamino acids defined above in the form of a mono-, di- or trialkanolamine salt is used.
Bei der Zugabe einer solchen wasserfreien Mischung zur wäßrigen Flotte wird das Siliconöl in der wäßrigen Phase von selbst durch das verwendete Salz emulgiert.When such an anhydrous mixture is added to the aqueous liquor, the silicone oil in the aqueous phase is automatically emulsified by the salt used.
Es wird darauf hingewiesen, daß als zu verwendendes Konzentrat die oben definierte wäßrige Emulsion bevorzugt ist.It should be noted that the aqueous emulsion defined above is preferred as the concentrate to be used.
Die erfindungsgemäße Hydrophobierung kann mit einem bekannten Hydrophobierungsmittel beispielsweise auf der Basis einer Paraffin- oder Wachsemulsion kombiniert werden, d.h. gleichzeitig oder im Anschluß an eine in wäßriger Flotte üblichen Hydrophobierung. Dabei wird eine deutliche Verbesserung der Hydrophobierungseffekte erreicht.The hydrophobization according to the invention can be combined with a known hydrophobizing agent, for example based on a paraffin or wax emulsion, i.e. at the same time or following a hydrophobization which is customary in aqueous liquors. A significant improvement in the water repellency effects is achieved.
Die oben beschriebenen Konzentrate können, bezogen auf das Gesamtgewicht der Mischung, zusätzlich 5 bis 45, bevorzugt 10 bis 30, Gew.% festes und/oder flüssiges Paraffin, beispielsweise Paraffin mit einem Schmelzpunkt von 20 bis 100°C, Paraffinöl oder Weißöl, eines natürlichen Fettes oder Öles, wie Fischtran oder Knochenöl, oder eines synthetischen oder natürlichen Wachses, wie Polyethylenwachse, Polyisobutylenwachse, Bienenwachs oder Karnaubawachs, enthalten, wobei zweckmäßigerweise das Gewichtsverhältnis Siliconöl zu Paraffin den Wert von 1:1 nicht überschreitet. Für eine solche Kombination sind besonders bevorzugt festes Paraffin mit einem Schmelzpunkt zwischen 40 und 60°C und Weißöl. Die angegebenen Mengen an Paraffin, Fetten, Ölen oder Wachsen werden von den Konzentraten problemlos aufgenommen.The concentrates described above can, based on the total weight of the mixture, additionally 5 to 45, preferably 10 to 30,% by weight of solid and / or liquid paraffin, for example paraffin with a melting point of 20 to 100 ° C., paraffin oil or white oil, one contain natural fats or oils, such as fish oil or bone oil, or a synthetic or natural wax, such as polyethylene waxes, polyisobutylene waxes, beeswax or carnauba wax, the weight ratio of silicone oil to paraffin expediently not exceeding the value of 1: 1. Solid paraffin with a melting point between 40 and 60 ° C. and white oil are particularly preferred for such a combination. The specified amounts of paraffin, fats, oils or waxes are easily absorbed by the concentrates.
Bei der praktischen Anwendung wird während oder anschließend an die Nachgerbung gegebenenfalls zusammen mit Farbstoffen ein oben bezeichnetes Konzentrat, bezogen auf das Falzgewicht des Leders oder Naßgewicht der Pelze, in einer Menge von 0,5 bis 20 Gew.%, bevorzugt 2 bis 10 Gew.%, verwendet. Zweckmäßigerweise wird dabei das verwendete Konzentrat im Verhältnis 1:2 bis 1:5 mit Wasser verdünnt und der Arbeitsflotte zugegeben.In practical use, an above-mentioned concentrate, based on the shaved weight of the leather or wet weight of the furs, in an amount of 0.5 to 20% by weight, preferably 2 to 10% by weight, optionally together with dyes, during or after the retanning. % used. The concentrate used is expediently diluted with water in a ratio of 1: 2 to 1: 5 and added to the working liquor.
Die erfindungsgemäße Hydrophobierung kann auch zweistufig während und nach der Nachgerbung erfolgen. Zweckmäßige Gerbstoffe für die Nachgerbung sind vegetabilische Gerbstoffe und synthetische Gerbstoffe, beispielsweise auf der Basis von Phenolsulfonsäure-Formaldehyd-Kondensaten. Als Farbstoffe, die gleichzeitig mitverwendet werden können, kommen beispielsweise die üblichen verwendeten sauren, substantiven oder basischen Anilinfarbstoffe in Betracht.The hydrophobization according to the invention can also be carried out in two stages during and after retanning. Useful tanning agents for retanning are vegetable tanning agents and synthetic tanning agents, for example based on phenolsulfonic acid-formaldehyde condensates. Suitable dyes which can be used simultaneously are, for example, the customary acidic, substantive or basic aniline dyes.
Die eigentliche erfindungsgemäße Hydrophobierung während oder nach der Nachgerbung erfolgt unter Walken in einer geeigneten Vorrichtung in an sich üblicher Weise: d.h. bei Flottenlängen von 50 bis 2.000 %, bevorzugt 100 bis 400 %, bezogen auf das Falzgewicht des Leders oder Naßgewicht der Pelze, Temperaturen von 20 bis 60°C, bevorzugt 35 bis 50°C, wobei zu Beginn die pH-Werte in der Regel zwischen 4,5 und 8,0, bevorzugt 4,8 bis 5,5, liegen. Im allgemeinen ist die Hydrophobierung in einer Zeit zwischen 20 bis 240, bevorzugt 30 bis 120 Minuten, beendet.The actual hydrophobization according to the invention during or after retanning is carried out by milling in a suitable device usual way: ie with fleet lengths of 50 to 2,000%, preferably 100 to 400%, based on the fold weight of the leather or wet weight of the furs, temperatures of 20 to 60 ° C, preferably 35 to 50 ° C, with the pH at the beginning -Values are generally between 4.5 and 8.0, preferably 4.8 to 5.5. In general, the hydrophobization is completed in a time between 20 to 240, preferably 30 to 120 minutes.
Am Ende der Hydrophobierung wird der Emulgator mit Säure, bevorzugt Ameisensäure, fixiert, indem ein pH-Wert von 3,0 bis 5,0, bevorzugt 3,8 bis 4,0, eingestellt wird.At the end of the hydrophobization, the emulsifier is fixed with acid, preferably formic acid, by adjusting a pH of 3.0 to 5.0, preferably 3.8 to 4.0.
Die Wirkung der Hydrophobierung kann durch eine Nachbehandlung mit einem in der Gerberei üblichen zwei-, drei- oder vierwertigen Metallsalz, insbesondere mit einem basischen Chromsulfat, mit Aluminiumsulfat, Zirkon-, Titansulfat, Calciumchlorid oder Magnesiumsulfat, verstärkt werden.The effect of the hydrophobization can be enhanced by an aftertreatment with a tetravalent, normal or tetravalent metal salt, in particular with a basic chromium sulfate, with aluminum sulfate, zirconium, titanium sulfate, calcium chloride or magnesium sulfate.
Von den genannten Salzen werden zweckmäßigerweise, bezogen auf das Falzgewicht des Leders oder Naßgewicht der Pelze, 0,5 bis 5 Gew.%, bevorzugt 1 bis 2 Gew.%, eingesetzt. Von den angegebenen Salzen sind basische Chromsulfate und Aluminiumsulfat bevorzugt.Of the salts mentioned, 0.5 to 5% by weight, preferably 1 to 2% by weight, is expediently used, based on the shaved weight of the leather or wet weight of the furs. Of the specified salts, basic chromium sulfate and aluminum sulfate are preferred.
Teile sind Gewichtsteile, Prozentangaben beziehen sich, soweit nicht anders vermerkt, auf das Gewicht.Parts are parts by weight, percentages relate to the weight, unless stated otherwise.
49,2 Teile eines Dimethylpolysiloxans, bei dem 3 % der Methylgruppen in der Kette durch Mercaptopropyl ersetzt sind, mit der Viskosität von 150 mPa·s und 9,8 Teile N-Oleoyl-sarkosin (Ölsäuresarkosid) werden unter Rühren gemischt und auf 60°C erwärmt. Dann wird eine auf 60°C erwärmte Mischung von 37,2 Teilen Wasser und 1,8 Teilen 50 %iger wäßriger Natronlauge unter Rühren langsam zugegeben. Die vollständige Umsetzung zum Natriumsalz zeigt sich darin, daß sich ein konstanter pH-Wert einstellt. Anschließend wird der pH-Wert der Mischung auf 7,5 bis 8,0 eingestellt. Die fertige Mischung läßt man unter Rühren abkühlen.49.2 parts of a dimethylpolysiloxane, in which 3% of the methyl groups in the chain are replaced by mercaptopropyl, with a viscosity of 150 mPa · s and 9.8 parts of N-oleoyl-sarcosine (oleic acid sarcoside) are mixed with stirring and to 60 ° C warmed. A mixture of 37.2 parts of water and 1.8 parts of 50% strength aqueous sodium hydroxide solution, heated to 60 ° C., is then slowly added with stirring. The complete conversion to the sodium salt is shown by the fact that a constant pH is established. The pH of the mixture is then adjusted to 7.5 to 8.0. The finished mixture is allowed to cool with stirring.
79,0 Teile eines Dimethylpolysiloxans, bei dem 3 % der Methylgruppen in der Kette durch Mercaptopropyl ersetzt sind, mit einer Viskosität von 150 mPa·s und 15 Teile N-Oleoyl-sarkosin werden gemischt und die Mischung wird unter Rühren auf 60°C erwärmt. Dann werden bei 60°C unter Rühren 6,0 Teile Diethanolamin (100 %ig) zugegeben. Die fertige Mischung läßt man unter Rühren abkühlen.79.0 parts of a dimethylpolysiloxane, in which 3% of the methyl groups in the chain are replaced by mercaptopropyl, with a viscosity of 150 mPa · s and 15 parts of N-oleoyl-sarcosine are mixed and the mixture is heated to 60 ° C. with stirring . Then 6.0 parts of diethanolamine (100%) are added at 60 ° C. with stirring. The finished mixture is allowed to cool with stirring.
41,3 Teile Wasser und 3,7 Teile wäßrige 25 %ige Natronlauge werden gemischt und auf 60°C erwärmt. In die verdünnte Natronlauge wird eine vorher auf 60°C erwärmte Mischung aus 30,0 Teilen eines Dimethylpolysiloxans, bei dem 3 % der Methylgruppen durch Mercaptopropyl ersetzt sind, mit einer Viskosität von 180 mPa·s, 6,0 Teilen festes Paraffin vom Schmelzpunkt von 52 bis 54°C, 9,5 Teilen Weißöl und 9,5 Teilen N-Oleoyl-sarkosin eingerührt. Es wird bei 60°C gerührt, bis der pH-Wert konstant bleibt. Anschließend wird der pH-Wert der Mischung auf 7,5 bis 8,0 eingestellt. Die Abkühlung der Mischung erfolgt unter Rühren.41.3 parts of water and 3.7 parts of aqueous 25% sodium hydroxide solution are mixed and heated to 60.degree. A mixture of 30.0 parts of a dimethylpolysiloxane, in which 3% of the methyl groups have been replaced by mercaptopropyl, with a viscosity of 180 mPa · s, 6.0 parts of solid paraffin with a melting point of 6.0 parts, is warmed into the dilute sodium hydroxide solution 52 to 54 ° C, 9.5 parts of white oil and 9.5 parts of N-oleoyl sarcosine stirred. The mixture is stirred at 60 ° C until the pH remains constant. The pH of the mixture is then adjusted to 7.5 to 8.0. The mixture is cooled with stirring.
200 Teile des in Beispiel 1 charakterisierten Dimethylpolysiloxans und 40 Teile N-Stearoyl-sarkosin (Stearinsäuresarkosid) werden unter Rühren gemischt und auf 60°C erwärmt. Dann wird eine auf 60°C erwärmte Mischung von 160 Teilen Wasser und 8 Teilen 50 %iger wäßriger Natronlauge unter Rühren langsam zugegeben. Nach Einstellen des pH-Wertes auf 7,5-8 mit 50 %iger Natronlauge läßt man die Mischung unter Rühren abkühlen.200 parts of the dimethylpolysiloxane characterized in Example 1 and 40 parts of N-stearoyl sarcosine (stearic acid sarcoside) are mixed with stirring and heated to 60 ° C. A mixture of 160 parts of water and 8 parts of 50% strength aqueous sodium hydroxide solution, heated to 60 ° C., is then slowly added with stirring. After adjusting the pH to 7.5-8 with 50% sodium hydroxide solution, the mixture is allowed to cool with stirring.
200 Teile des in Beispiel 1 charakterisierten Dimethylpolysiloxans und 40 Teile N-Lauroyl-sarkosin (Laurinsäuresarkosid) werden unter Rühren gemischt und auf 60°C erwärmt. Dann wird eine auf 60°C erwärmte Mischung von 160 Teilen Wasser und 8 Teilen 50 %iger wäßriger Natronlauge unter Rühren langsam zugegeben. Nach Einstellen des pH-Wertes auf 7,5-8 mit 50 %iger Natronlauge läßt man die Mischung unter Rühren abkühlen.200 parts of the dimethylpolysiloxane characterized in Example 1 and 40 parts of N-lauroyl sarcosine (lauric acid sarcoside) are mixed with stirring and heated to 60.degree. A mixture of 160 parts of water and 8 parts of 50% strength aqueous sodium hydroxide solution, heated to 60 ° C., is then slowly added with stirring. After adjusting the pH to 7.5-8 with 50% sodium hydroxide solution, the mixture is allowed to cool with stirring.
200 Teile des in Beispiel 1 charakterisierten Dimethylpolysiloxans und 40 Teile N-Isononanoyl-sarkosin (Isononansäuresarkosid) werden unter Rühren gemischt und auf 60°C erwärmt. Dann wird eine auf 60°C erwärmte Mischung von 160 Teilen Wasser und 12 Teilen 50 %iger wäßriger Natronlauge unter Rühren langsam zugegeben. Unter Rühren läßt man die Mischung abkühlen.200 parts of the dimethylpolysiloxane characterized in Example 1 and 40 parts of N-isononanoyl-sarcosine (isononanoic acid sarcoside) are added Stir mixed and heated to 60 ° C. A mixture of 160 parts of water and 12 parts of 50% strength aqueous sodium hydroxide solution, heated to 60 ° C., is then slowly added with stirring. The mixture is allowed to cool with stirring.
160 Teile des in Beispiel 1 charakterisierten Dimethylpolysiloxans und 40 Teile N-Oleyl-sarkosin (Ölsäuresarkosid) werden unter Rühren gemischt und auf 60°C erwärmt. Dann wird eine auf 60°C erwärmte Mischung von 160 Teilen Wasser und 17,5 Teilen Triethanolamin unter Rühren langsam zugegeben. Unter Rühren läßt man die Mischung abkühlen.160 parts of the dimethylpolysiloxane characterized in Example 1 and 40 parts of N-oleyl sarcosine (oleic acid sarcoside) are mixed with stirring and heated to 60 ° C. Then a mixture of 160 parts of water and 17.5 parts of triethanolamine heated to 60 ° C. is slowly added with stirring. The mixture is allowed to cool with stirring.
Herstellung von Siliconöl-Emulsionen:
50,0 Teile eines erfindungsgemäß zu verwendenden handelsüblichen Polysiloxans werden mit 10,0 Teilen N-Oleoyl-sarkosin unter Rühren gemischt und auf 60°C erwärmt. Dann wird eine auf 60°C erwärmte Mischung von 36 Teilen Wasser und 4 Teilen 25 %ige wäßrige Natronlauge unter Rühren langsam zugegeben. Durch Rühren bis zur Konstanz des pH-Wertes wird die vollständige Umsetzung zum Natriumsalz erreicht. Anschließend wird der pH-Wert der Mischung auf 7,8 bis 8,0 eingestellt und unter Rühren auf Raumtemperatur abgekühlt.Production of silicone oil emulsions:
50.0 parts of a commercially available polysiloxane to be used according to the invention are mixed with 10.0 parts of N-oleoyl-sarcosine with stirring and heated to 60.degree. Then a mixture of 36 parts of water and 4 parts of 25% aqueous sodium hydroxide solution heated to 60 ° C. is slowly added with stirring. The complete conversion to the sodium salt is achieved by stirring until the pH is constant. The pH of the mixture is then adjusted to 7.8 to 8.0 and cooled to room temperature with stirring.
Eine Arbeitsweise, bei der die Mischung aus Wasser und Natronlauge vorgelegt und die Mischung aus Siliconöl und N-Oleoyl-sarkosin unter Rühren zugegeben wird, führt zum gleichen Ergebnis.A procedure in which the mixture of water and sodium hydroxide solution is initially introduced and the mixture of silicone oil and N-oleoyl-sarcosine is added with stirring leads to the same result.
Als handelsübliches Polysiloxan wurden verwendet im Beispiel 8 ein Dimethylpolysiloxan mit einer Viskosität von ca. 95 mPa·s, im Beispiel 9 ein Phenylmethyl-Polysiloxan mit einer Viskosität von ca. 95 mPa·s, im Beispiel 10 ein aminofunktionelles Dimethylpolysiloxan mit einer Aminzahl von etwa 0,8 bis 1,0 und einer Viskosität von 30 bis 50 mPa·s und im Beispiel 11 ein Dimethylpolysiloxan mit 4 Carboxylgruppen im Molekül.The commercially available polysiloxane used in Example 8 was a dimethylpolysiloxane with a viscosity of approximately 95 mPa · s, in Example 9 a phenylmethyl polysiloxane with a viscosity of approximately 95 mPa · s, in Example 10 an amino-functional dimethylpolysiloxane with an amine number of approximately 0.8 to 1.0 and a viscosity of 30 to 50 mPa · s and in Example 11 a dimethylpolysiloxane with 4 carboxyl groups in the molecule.
Chromvorgegerbte Rindleder von der Falzstärke 2,2 mm, die auf einen pH-Wert von 5,0 bis 6,0 entsäuert wurden, werden, bezogen auf das Falzgewicht, mit 5 Gew.% handelsüblichen Mimosaextrakts, 3 Gew.% eines handelsüblichen synthetischen Gerbstoffes auf Basis Phenolsulfonsäure-Formaldehyd-Kondensat, 1 Gew.% eines handelsüblichen Anilinfarbstoffs und 5 Gew.% der unter Beispiel 1 angegebenen Silikonölemulsion 1,5 Stunden im Gerbfaß bei 40°C gewalkt, wobei der pH-Wert der Behandlungsflotte von 100 % 5,2 bis 5,5 beträgt.Chromium pre-tanned cowhide with a fold thickness of 2.2 mm, which has been deacidified to a pH value of 5.0 to 6.0, based on the fold weight, with 5% by weight of commercially available mimosa extract and 3% by weight of a commercially available synthetic tanning agent based on phenolsulfonic acid-formaldehyde condensate, 1% by weight of a commercially available aniline dye and 5% by weight of the silicone oil emulsion specified in Example 1, drummed for 1.5 hours in a tanning drum at 40 ° C., the pH of the treatment liquor being 100% 5. Is 2 to 5.5.
Anschließend wird mit 85 %iger Ameisensäure auf einen pH-Wert von 4,5 abgesäuert, 30 min gewalkt und danach mit Wasser von 40°C 10 min gewaschen.It is then acidified to a pH of 4.5 with 85% formic acid, drummed for 30 minutes and then washed with water at 40 ° C. for 10 minutes.
In das frische Bad von 100 % Wasser und 40°C werden weitere 3 Gew.%, bezogen auf das Falzgewicht, der unter Beispiel 1 angegebenen Silikonemulsion innerhalb von 30 min in das Leder eingewalkt. Es wird mit 85 %iger Ameisensäure auf einen pH-Wert von 3,8 bis 4,0 abgesäuert und mit 2 Gew.% eines handelsüblichen Chromgerbstoffes (Cr₂O₃-Gehalt von 25 % und einer Basizität von 33 %) 90 min lang bei 40°C fixiert. Anschließend werden die Leder gewaschen, mechanisch ausgereckt und getrocknet.In the fresh bath of 100% water and 40 ° C., a further 3% by weight, based on the shaved weight, of the silicone emulsion specified in Example 1 is rolled into the leather within 30 minutes. It is acidified with 85% formic acid to a pH of 3.8 to 4.0 and with 2% by weight of a commercially available chrome tanning agent (Cr₂O₃ content of 25% and a basicity of 33%) for 90 minutes at 40 ° C fixed. The leathers are then washed, mechanically stretched and dried.
Die Prüfung im Bally-Penetrometer bei 15 % Stauchung ergab folgende Werte:
Chromgegerbte und auf einen pH-Wert von 5,0 bis 6,0 entsäuerte Rindleder werden, jeweils bezogen auf das Falzgewicht des Leders, mit 5 Gew.% Kastanienholzextrakt, 3 Gew.% eines handelsüblichen synthetischen Gerbstoffes auf Basis Naphthalinsulfosäure-Formaldehyd-Kondensat, 1 Gew.% Anilinfarbstoff und einer Mischung von 6 % eines handelsüblichen Hydrophobierungsmittels für Leder auf Basis einer Paraffinemulsion und 3 Gew.% Silikonölemulsion gemäß Beispiel 2 2 Stunden lang gewalkt.Chromium-tanned and deacidified to a pH value of 5.0 to 6.0, each based on the shaved weight of the leather, with 5% by weight of chestnut wood extract, 3% by weight of a commercially available synthetic tanning agent based on naphthalenesulfonic acid-formaldehyde condensate, 1% by weight of aniline dye and a mixture of 6% of a commercially available hydrophobizing agent for leather based on a paraffin emulsion and 3% by weight of silicone oil emulsion according to Example 2 for 2 hours.
Anschließend wird mit Ameisensäure auf einen pH-Wert von 3,8 bis 4,0 abgesäuert und weitere 90 min mit einem handelsüblichen Chromgerbstoff (Chromoxid-Gehalt ca. 25 %, Basizität ca. 33 %) fixiert. Nach dem Auswaschen erfolgt die übliche Trocknung.It is then acidified to a pH of 3.8 to 4.0 with formic acid and fixed for a further 90 min with a commercially available chrome tanning agent (chromium oxide content approx. 25%, basicity approx. 33%). After washing out, the usual drying takes place.
Die Prüfung im Bally-Penetrometer bei 15 % Stauchung ergab folgende Werte:
Chromgegerbte Rindleder (wetblue) werden nach der Entsäuerung auf pH 5,0 bis 6,0 zur Nachgerbung mit, jeweils bezogen auf das Falzgewicht des Leders, 7,5 Gew.% eines Gemisches von vegetabilischen und synthetischen handelsüblichen Gerbstoffen auf Basis von Naphthalinsulfosäure-Formaldehyd-Kondensat, 1,5 Gew.% eines handelsüblichen Anilinfarbstoffes und mit 7 Gew.% eines üblichen Hydrophobierungsmittels für Leder auf Basis einer Paraffinemulsion 60 min im Faß gewalkt und anschließend weitere 30 min lang mit 3 Gew.% der Silikonölemulsion gemäß Beispiel 1 im Faß gewalkt. Unter weiterem 30minütigem Walken wird auf einen pH-Wert von 4,0 mit Ameisensäure abgesäuert und mit 1,5 Gew.% handelsüblichen Chromgerbstoffes innerhalb von 90 min fixiert.Chromium-tanned cowhide (wet blue) is used for post-tanning after deacidification to pH 5.0 to 6.0, each based on the shaved weight of the leather, 7.5% by weight of a mixture of vegetable and synthetic commercial tannins based on naphthalenesulfonic acid-formaldehyde -Condensate, 1.5% by weight of a commercially available aniline dye and 7% by weight of a customary water repellent for leather based on a paraffin emulsion, drummed for 60 minutes in the drum and then for a further 30 minutes with 3% by weight of the silicone oil emulsion according to Example 1 in the drum tumbled. With further walking for 30 minutes, the mixture is acidified to a pH of 4.0 with formic acid and fixed with 1.5% by weight of commercially available chromium tanning agent within 90 minutes.
Die Leder werden wie üblich gespült und getrocknet.The leather is rinsed and dried as usual.
Die Prüfung im Bally-Penetrometer bei 15 % Stauchung ergab folgende Werte:
Die mit handelsüblichen Entsäuerungsmitteln auf einen pH-Wert von 5,0 bis 6,0 entsäuerten wetblue-Leder werden, wie unter Beispiel A angegeben, nachgegerbt, gefärbt und mit, jeweils bezogen auf das Falzgewicht, 8 Gew.% eines handelsüblichen, nicht-hydrophobierend wirkenden Fettlickergemischs gefettet, abgesäuert auf einen pH-Wert von 4,0 und gespült.The wetblue leathers deacidified to a pH of 5.0 to 6.0 with commercially available deacidifying agents are retanned, dyed, as indicated in Example A, and with, based on the shaved weight, 8% by weight of a commercially available, non- Fat-repellent mixture with a hydrophobic effect, greased, acidified to a pH of 4.0 and rinsed.
Anschließend wird in frischer Flotte (100 %, 40°C) 30 min lang mit 4 Gew.% der unter Beispiel 3 beschriebenen Silikonölemulsion mit Paraffin und Weißöl gewalkt und mit 1,5 Gew.% handelsüblichen Chromgerbstoffes 60 min lang fixiert.The mixture is then drummed in fresh liquor (100%, 40 ° C.) for 30 minutes with 4% by weight of the silicone oil emulsion described in Example 3 with paraffin and white oil and fixed with 1.5% by weight of commercially available chrome tanning agent for 60 minutes.
Nach dem Auswaschen und Ausrecken erfolgt die übliche Trocknung.After washing and stretching, the usual drying takes place.
Bei der Prüfung im Bally-Penetrometer bei 15 % Stauchung wurden folgende Werte festgestellt:
Die auf einen pH-Wert von 5,0 bis 6,0 entsäuerten chromgegerbten Leder werden wie im Beispiel A mit, jeweils bezogen auf das Falzgewicht des Leders, 7 Gew.% eines Gemisches handelsüblicher vegetabilischer und synthetischer Gerbstoffe auf Basis von Phenolkondensat nachgegerbt, mit 1,2 Gew.% Anilinfarbstoff gefärbt und mit 5 Gew.% handelsüblichen, nicht-hydrophobierend wirkendem Fettlicker während 40 min gefettet.The chrome-tanned leather, deacidified to a pH of 5.0 to 6.0, is retanned with 7% by weight of a mixture of commercially available vegetable and synthetic tanning agents based on phenol condensate, based in each case on the shaved weight of the leather 1.2% by weight of aniline dye and greased with 5% by weight of commercially available, non-hydrophobic grease licker for 40 minutes.
Danach wird mit einer Mischung aus 3 Gew.% der unter Beispiel 1 angegebenen Silikonölemulsion und 3 Gew.% eines handelsüblichen Hydrophobierungsmittels auf der Basis Paraffinemulsion weitere 60 min gewalkt, auf pH 3,8 bis 4,0 abgesäuert, 30 min lang, und mit 5 Gew.% eines handelsüblichen Aluminiumsalzes (Al₂SO₄)₃·18 H₂O 60 min fixiert, ausgewaschen und wie üblich ausgereckt und getrocknet.The mixture is then drummed with a mixture of 3% by weight of the silicone oil emulsion specified in Example 1 and 3% by weight of a commercially available hydrophobicizing agent based on paraffin emulsion, acidified to pH 3.8 to 4.0, for 30 minutes and with 5 wt.% Of a commercially available aluminum salt (Al₂SO₄) ₃ · 18 H₂O fixed for 60 min, washed out and stretched and dried as usual.
Die Prüfung im Bally-Penetrometer bei 15 % Stauchung ergab folgende Werte:
Die vorgenommenen Prüfungen im Bally-Penetrometer zeigen deutlich verbesserte Wasserresistenz bei der dynamischen Prüfung bis zum Durchtritt des ersten Wassertropfens und eine erhebliche Verringerung der Wasseraufnahme der Leder gegenüber dem bisher üblichen Hydrophobierungsverfahren.The tests carried out in the Bally penetrometer show significantly improved water resistance in the dynamic test up to the passage of the first drop of water and a considerable reduction in the water absorption of the leather compared to the previously usual hydrophobization process.
Es wird gemäß Beispiel A verfahren.The procedure is as in Example A.
Prüfung der behandelten Leder im Bally-Penetrometer bei 15 % Stauchung ergab folgende Werte.
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853529869 DE3529869A1 (en) | 1985-08-21 | 1985-08-21 | METHOD FOR HYDROPHOBIZING LEATHER AND FURS |
DE3529869 | 1985-08-21 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0213480A2 true EP0213480A2 (en) | 1987-03-11 |
EP0213480A3 EP0213480A3 (en) | 1987-10-28 |
EP0213480B1 EP0213480B1 (en) | 1989-01-25 |
Family
ID=6278985
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86111130A Expired EP0213480B1 (en) | 1985-08-21 | 1986-08-12 | Method of water-proofing leather and furs |
Country Status (6)
Country | Link |
---|---|
US (1) | US4701269A (en) |
EP (1) | EP0213480B1 (en) |
JP (1) | JPS6245700A (en) |
CA (1) | CA1255855A (en) |
DE (2) | DE3529869A1 (en) |
ES (1) | ES2001252A6 (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0280152A2 (en) * | 1987-02-26 | 1988-08-31 | Bayer Ag | Water-proofing agent for leather |
EP0324345A1 (en) * | 1988-01-12 | 1989-07-19 | BASF Aktiengesellschaft | Method for water-proofing leather, furs and synthetic leathers |
WO1995022627A2 (en) * | 1994-02-16 | 1995-08-24 | Basf Aktiengesellschaft | Water-proofing process for leathers and pelts by comb-like carboxylated polysiloxanes |
US5489389A (en) * | 1992-07-14 | 1996-02-06 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
US5567343A (en) * | 1992-07-14 | 1996-10-22 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
WO1996035814A1 (en) * | 1995-05-12 | 1996-11-14 | Stockhausen Gmbh & Co. Kg | Process for treating leathers with surfactants to improve their water-proofing |
EP0757108A2 (en) * | 1995-08-03 | 1997-02-05 | Rohm And Haas Company | Method for waterproofing leather |
US5683611A (en) * | 1994-01-12 | 1997-11-04 | Henkel Kommanditgesellschaft Auf Aktien | Preparations for the oiling of leather |
US5728313A (en) * | 1994-02-18 | 1998-03-17 | Henkel Corporation | Leather oiling compositions and their use |
DE102009047183A1 (en) | 2008-12-19 | 2010-07-15 | Basf Se | Dye mixture, useful for coloring leather, comprises a first anionic dye, a second anionic dye, and third anionic dye, where the first and third anionic dye are azo dyes, and the second anionic dye is the azo dye or napthalene-azo dye |
WO2011147959A2 (en) | 2010-05-28 | 2011-12-01 | Momentive Performance Materials Gmbh | Hydrophobizing of fibrous materials with polyorganosiloxanes |
DE102019115279B3 (en) * | 2019-06-06 | 2020-10-15 | Schill + Seilacher Gmbh | A method for producing a zinc derivative of an N-acylamino acid and its use |
US10947605B2 (en) | 2016-01-12 | 2021-03-16 | Fraunhofer-Gesellschaft Zur Forderung Der Angewand | Method for hydrophobising leather, and leather produced by means of same |
EP3981888A1 (en) | 2020-08-19 | 2022-04-13 | Schill + Seilacher GmbH | Finishing agent for leather |
WO2022154662A1 (en) | 2021-01-18 | 2022-07-21 | Stahl International B.V. | Composition and process for waterproofing leather |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5069935A (en) * | 1990-11-07 | 1991-12-03 | Wilson Sporting Goods Co. | Method of making water-repellent leather game ball |
DE4214150A1 (en) * | 1992-04-29 | 1993-11-11 | Stockhausen Chem Fab Gmbh | Process for the hydrophobization of materials of fibrous structure and means for carrying out the process |
DE4415062B4 (en) * | 1994-04-29 | 2004-04-01 | Stockhausen Gmbh & Co. Kg | Means and processes for waterproofing leather and furs |
US5972037A (en) * | 1995-07-26 | 1999-10-26 | Scheen Industries, Inc | Leather tanning processes and the products thereof |
US5911901A (en) * | 1995-10-04 | 1999-06-15 | Hodgson Process Chemicals, Inc. | Leather waterproofing method and composition |
PT102211B (en) * | 1998-10-14 | 2003-10-31 | Ibeji Investimentos E Servicos | TREATMENT FOR WATERPROOFING SKINS OF BOVINE ANIMALS DESIGNATEDLY BORN WITH CHROMIUM |
US6123632A (en) * | 1998-11-02 | 2000-09-26 | Spalding Sports Worldwide, Inc. | Game ball with improved moisture resistance |
DE19959949A1 (en) | 1999-12-13 | 2001-06-21 | Bayer Ag | Hydrophobization with carboxyl-containing polysiloxanes |
US7166235B2 (en) | 2002-05-09 | 2007-01-23 | The Procter & Gamble Company | Compositions comprising anionic functionalized polyorganosiloxanes for hydrophobically modifying surfaces and enhancing delivery of active agents to surfaces treated therewith |
US7025950B2 (en) | 2002-05-09 | 2006-04-11 | The Procter & Gamble Company | Oral care compositions comprising dicarboxy functionalized polyorganosiloxanes |
DE10242401A1 (en) * | 2002-09-12 | 2004-03-25 | Basf Ag | Fat liquoring agent for use with leather or hides comprises an oxidized sulfited and sulfated oil mixture, an emulsifier mixture and optionally also a dialkylsilanediol polymer and/or a sulfonated succinic acid, salt or ester |
DE10250111A1 (en) * | 2002-10-28 | 2004-05-06 | Bayer Ag | Chrome-free, waterproof leather |
DE102005029627A1 (en) * | 2005-06-23 | 2007-01-04 | Basf Ag | Process for the production of leather |
DE102006027400A1 (en) * | 2006-06-13 | 2007-12-20 | Wacker Chemie Ag | Process for treating proteinaceous fibrous matter with beta-ketocarbonyl-functional siloxane polymers |
US8138529B2 (en) | 2009-11-02 | 2012-03-20 | Transphorm Inc. | Package configurations for low EMI circuits |
EP2557181A1 (en) | 2011-08-12 | 2013-02-13 | LANXESS Deutschland GmbH | Method for hydrophobic finishing of substrates containing collagen fibre |
US8648643B2 (en) | 2012-02-24 | 2014-02-11 | Transphorm Inc. | Semiconductor power modules and devices |
US8803246B2 (en) | 2012-07-16 | 2014-08-12 | Transphorm Inc. | Semiconductor electronic components with integrated current limiters |
US9059076B2 (en) | 2013-04-01 | 2015-06-16 | Transphorm Inc. | Gate drivers for circuits based on semiconductor devices |
CN114622043B (en) * | 2022-04-13 | 2023-12-01 | 瑞泰(漳浦)皮业有限公司 | Manufacturing method of waterproof leather with head layer |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2047069A (en) * | 1930-05-09 | 1936-07-07 | Gen Aniline Works Inc | Amides |
US2964425A (en) * | 1958-04-29 | 1960-12-13 | Socony Mobil Oil Co Inc | Waterproofing of leathers |
CH524712A (en) * | 1970-11-20 | 1972-06-30 | Rhone Poulenc Sa | High stability aqueous alkylhydrogen polysiloxane emulsion |
FR2505866A1 (en) * | 1981-05-15 | 1982-11-19 | Elf Aquitaine | IMPROVED FUEL BASED ON HYDROCARBONS CONTAINING ALCOHOL |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2662039A (en) * | 1947-02-06 | 1953-12-08 | Harris Res Lab | Method of rendering organic textile material water repellent and composition therefor |
BE546491A (en) * | 1955-03-28 | |||
DE1266920B (en) * | 1959-07-18 | 1968-04-25 | Bayer Ag | Process for waterproofing leather |
NL301058A (en) * | 1963-01-21 | |||
DE1231432B (en) * | 1964-12-01 | 1966-12-29 | Boehme Fettchemie Gmbh | Water-soluble polymeric compounds as emulsifiers for emulsifying silicones in water |
GB1346070A (en) * | 1971-02-03 | 1974-02-06 | Dow Corning Ltd | Water repellent process and composition |
DE2439199A1 (en) * | 1974-08-16 | 1976-03-04 | Basf Ag | Aqueous silicone emulsions for fabric waterproofing - contg thermally decomposable emulsifiers |
DE3034380A1 (en) * | 1980-09-12 | 1982-03-25 | Th. Goldschmidt Ag, 4300 Essen | PREPARATION FOR SHRINKING WOOL |
-
1985
- 1985-08-21 DE DE19853529869 patent/DE3529869A1/en not_active Withdrawn
-
1986
- 1986-08-12 DE DE8686111130T patent/DE3661933D1/en not_active Expired
- 1986-08-12 EP EP86111130A patent/EP0213480B1/en not_active Expired
- 1986-08-13 US US06/895,686 patent/US4701269A/en not_active Expired - Lifetime
- 1986-08-14 CA CA000515970A patent/CA1255855A/en not_active Expired
- 1986-08-19 JP JP61192226A patent/JPS6245700A/en active Granted
- 1986-08-21 ES ES8601254A patent/ES2001252A6/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2047069A (en) * | 1930-05-09 | 1936-07-07 | Gen Aniline Works Inc | Amides |
US2964425A (en) * | 1958-04-29 | 1960-12-13 | Socony Mobil Oil Co Inc | Waterproofing of leathers |
CH524712A (en) * | 1970-11-20 | 1972-06-30 | Rhone Poulenc Sa | High stability aqueous alkylhydrogen polysiloxane emulsion |
FR2505866A1 (en) * | 1981-05-15 | 1982-11-19 | Elf Aquitaine | IMPROVED FUEL BASED ON HYDROCARBONS CONTAINING ALCOHOL |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0280152A3 (en) * | 1987-02-26 | 1990-02-28 | Bayer Ag | Water-proofing agent for leather |
EP0280152A2 (en) * | 1987-02-26 | 1988-08-31 | Bayer Ag | Water-proofing agent for leather |
EP0324345A1 (en) * | 1988-01-12 | 1989-07-19 | BASF Aktiengesellschaft | Method for water-proofing leather, furs and synthetic leathers |
US5741434A (en) * | 1992-07-14 | 1998-04-21 | Henkel Kommanditgesellschaft Auf Aktien | Leather oiling preparations and their use |
US5489389A (en) * | 1992-07-14 | 1996-02-06 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
US5567343A (en) * | 1992-07-14 | 1996-10-22 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
US5683611A (en) * | 1994-01-12 | 1997-11-04 | Henkel Kommanditgesellschaft Auf Aktien | Preparations for the oiling of leather |
AU683723B2 (en) * | 1994-02-16 | 1997-11-20 | Basf Aktiengesellschaft | Water-proofing process for leathers and pelts by comb-like carboxylated polysiloxanes |
WO1995022627A2 (en) * | 1994-02-16 | 1995-08-24 | Basf Aktiengesellschaft | Water-proofing process for leathers and pelts by comb-like carboxylated polysiloxanes |
US5702490A (en) * | 1994-02-16 | 1997-12-30 | Basf Aktiengesellschaft | Water repellent treatment of leather and skins with polysiloxanes functionalized with carboxyl groups in a comb-like manner |
WO1995022627A3 (en) * | 1994-02-16 | 1995-09-08 | Basf Ag | Water-proofing process for leathers and pelts by comb-like carboxylated polysiloxanes |
US5728313A (en) * | 1994-02-18 | 1998-03-17 | Henkel Corporation | Leather oiling compositions and their use |
WO1996035814A1 (en) * | 1995-05-12 | 1996-11-14 | Stockhausen Gmbh & Co. Kg | Process for treating leathers with surfactants to improve their water-proofing |
US5931970A (en) * | 1995-05-12 | 1999-08-03 | Stockhausen Gmbh & Co. Kg | Process for treating leathers with surfactants to improve water repellency |
EP0757108A3 (en) * | 1995-08-03 | 1998-03-18 | Rohm And Haas Company | Method for waterproofing leather |
EP0757108A2 (en) * | 1995-08-03 | 1997-02-05 | Rohm And Haas Company | Method for waterproofing leather |
DE102009047183A1 (en) | 2008-12-19 | 2010-07-15 | Basf Se | Dye mixture, useful for coloring leather, comprises a first anionic dye, a second anionic dye, and third anionic dye, where the first and third anionic dye are azo dyes, and the second anionic dye is the azo dye or napthalene-azo dye |
WO2011147959A2 (en) | 2010-05-28 | 2011-12-01 | Momentive Performance Materials Gmbh | Hydrophobizing of fibrous materials with polyorganosiloxanes |
US10947605B2 (en) | 2016-01-12 | 2021-03-16 | Fraunhofer-Gesellschaft Zur Forderung Der Angewand | Method for hydrophobising leather, and leather produced by means of same |
DE102019115279B3 (en) * | 2019-06-06 | 2020-10-15 | Schill + Seilacher Gmbh | A method for producing a zinc derivative of an N-acylamino acid and its use |
EP3981888A1 (en) | 2020-08-19 | 2022-04-13 | Schill + Seilacher GmbH | Finishing agent for leather |
WO2022154662A1 (en) | 2021-01-18 | 2022-07-21 | Stahl International B.V. | Composition and process for waterproofing leather |
NL2027334B1 (en) | 2021-01-18 | 2022-07-25 | Stahl Int B V | Composition and process for waterproofing leather |
Also Published As
Publication number | Publication date |
---|---|
ES2001252A6 (en) | 1988-05-01 |
US4701269A (en) | 1987-10-20 |
EP0213480A3 (en) | 1987-10-28 |
CA1255855A (en) | 1989-06-20 |
DE3661933D1 (en) | 1989-03-02 |
DE3529869A1 (en) | 1987-02-26 |
JPH0575040B2 (en) | 1993-10-19 |
JPS6245700A (en) | 1987-02-27 |
EP0213480B1 (en) | 1989-01-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0213480B1 (en) | Method of water-proofing leather and furs | |
EP0324345B1 (en) | Method for water-proofing leather, furs and synthetic leathers | |
EP0745141B1 (en) | Water-proofing process for leathers and pelts by comb-like carboxylated polysiloxanes | |
DE19646916C1 (en) | Use of carboxyamide polysiloxanes for hydrophobizing materials with a fibrous structure and process for carrying them out | |
EP0602071B1 (en) | Aqueous dispersions of novel amphiphilic co-oligomers for imparting a washing and cleaning-resistant finish to leather and pelts and their use | |
EP0800589B1 (en) | Agents and process for waterproofing leather and hides | |
EP0638128B1 (en) | Process and agents for waterproofing materials having a fibrous structure | |
DE69020680T2 (en) | Use of fluorochemicals in leather manufacturing. | |
EP1896620B1 (en) | Method for producing leather | |
DE4142318C2 (en) | Use of fatty acid conversion products in leather and fur greasing agents and agents for greasing leather and fur skins | |
EP0280152B1 (en) | Water-proofing agent for leather | |
DE1800244C2 (en) | Process for the simultaneous greasing and impregnation of leather | |
DE10028142B4 (en) | Processes for pimples and chrome tanning | |
EP0752011B1 (en) | Use of dimeric and/or trimeric aminopropionic acids for oiling off of leathers | |
DE3717961C2 (en) | Process for the preparation of mixtures of N, N-disubstituted ß-aminopropionic acid derivatives, certain mixtures of N-alkyl-N (2-carboxyethyl) sulfonamides and N-alkyl-N (2-carboxyethyl) ureas and use of the compounds mentioned | |
DE2355503C3 (en) | Process for the production of a fatty chrome tanning agent and its use for tanning and retanning | |
EP1597402B1 (en) | Method for hydrophobing leather and furskins | |
EP0752010B1 (en) | Use of alkylene diamine tetrapropionic acids for the oiling off of leathers | |
DE864905C (en) | Fatliquor | |
DE907339C (en) | Process for tanning and greasing animal skins | |
DE2355503B2 (en) | Process for the production of a fatty chrome tanning agent and its use for tanning and retanning | |
EP1621640A1 (en) | Agent for the hydrophobic treatment of leather | |
DE3248485A1 (en) | Process for retanning leathers | |
DE3504308A1 (en) | Process for the simultaneous fat-liquoring and water-repellent finishing of tanned leather | |
WO1995019452A1 (en) | Use of aminopropionic acid derivatives for the fatty treatment of leather |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): CH DE FR GB IT LI |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): CH DE FR GB IT LI |
|
17P | Request for examination filed |
Effective date: 19870924 |
|
17Q | First examination report despatched |
Effective date: 19880601 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): CH DE FR GB IT LI |
|
ITF | It: translation for a ep patent filed | ||
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
REF | Corresponds to: |
Ref document number: 3661933 Country of ref document: DE Date of ref document: 19890302 |
|
ET | Fr: translation filed | ||
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: CHEMISCHE FABRIK STOCKHAUSEN GMBH Effective date: 19891020 |
|
26 | Opposition filed |
Opponent name: BAYER AG, LEVERKUSEN KONZERNVERWALTUNG RP PATENTE Effective date: 19891024 Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN Effective date: 19891023 Opponent name: CHEMISCHE FABRIK STOCKHAUSEN GMBH Effective date: 19891020 |
|
ITTA | It: last paid annual fee | ||
APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
PLBN | Opposition rejected |
Free format text: ORIGINAL CODE: 0009273 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: OPPOSITION REJECTED |
|
27O | Opposition rejected |
Effective date: 19980203 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19990715 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19990723 Year of fee payment: 14 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000831 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000831 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010430 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20050804 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20050810 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20050829 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20060811 |