EP0024014A1 - Procédé de retannage de cuirs tannés au minéral avec des acides sulfoniques aromatiques - Google Patents
Procédé de retannage de cuirs tannés au minéral avec des acides sulfoniques aromatiques Download PDFInfo
- Publication number
- EP0024014A1 EP0024014A1 EP80104522A EP80104522A EP0024014A1 EP 0024014 A1 EP0024014 A1 EP 0024014A1 EP 80104522 A EP80104522 A EP 80104522A EP 80104522 A EP80104522 A EP 80104522A EP 0024014 A1 EP0024014 A1 EP 0024014A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- leather
- terphenyl
- retanning
- alkali
- agents
- 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
- 238000000034 method Methods 0.000 title claims abstract description 7
- 239000010985 leather Substances 0.000 title description 38
- -1 aromatic sulfonic acids Chemical class 0.000 title description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 title description 3
- 239000011707 mineral Substances 0.000 title description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 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 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 21
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 13
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 125000006267 biphenyl group Chemical group 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- FDLFMPKQBNPIER-UHFFFAOYSA-N 1-methyl-3-(3-methylphenoxy)benzene Chemical compound CC1=CC=CC(OC=2C=C(C)C=CC=2)=C1 FDLFMPKQBNPIER-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 235000021190 leftovers Nutrition 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 2
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 125000000129 anionic group Chemical group 0.000 description 11
- 238000004043 dyeing Methods 0.000 description 8
- 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 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 235000018553 tannin Nutrition 0.000 description 4
- 229920001864 tannin Polymers 0.000 description 4
- 239000001648 tannin Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- AQWAQMZZGDSQNM-UHFFFAOYSA-N 3,4-bis(4-sulfophenyl)benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C1=CC=C(S(O)(=O)=O)C=C1C1=CC=C(S(O)(=O)=O)C=C1 AQWAQMZZGDSQNM-UHFFFAOYSA-N 0.000 description 2
- 241001070941 Castanea Species 0.000 description 2
- 235000014036 Castanea Nutrition 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229940077464 ammonium ion Drugs 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000434 metal complex dye Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 229910006127 SO3X Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001887 acacia decurrens willd. var. dealbata absolute Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 description 1
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 1
- 239000011696 chromium(III) sulphate Substances 0.000 description 1
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
- D06P1/621—Compounds without nitrogen
- D06P1/622—Sulfonic acids or their salts
- D06P1/625—Aromatic
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/32—Material containing basic nitrogen containing amide groups leather skins
Definitions
- the isomeric mono- and disulfonic acids of diphenyl, terphenyl, diphenyl ether and ditolyl ether and their alkali and ammonium salts are preferably used.
- sulfonic acids of other non-crosslinked aromatic hydrocarbons in various leather manufacturing processes for example naphthalene and toluene, as auxiliaries for decalcifying raw material (GB-PS 8096) or in the form of their chromium III salts for tanning (DE-PS 627 110 and 643 088) is already known.
- the alkali metal salts of the mono- and disulfonic acids of benzene and naphthalene have also already been proposed for the preservation and improvement of the storage stability of mineral-soft, undyed leather in a moist or dry state (DE-PS 578 785).
- aromatic sulfonic acids as non-swelling acids to acidify the skin material prior to tanning is state of the art (see Ullmanns Enzyklopadie der Technische Chemie, 4th edition; volume 16, page 120).
- Commonly used as retanning agents and as auxiliaries for leveling chemical and / or physical irregularities in the leather surface are, for example, formaldehyde condensation products of ⁇ -naphthalenesulfonic acid (DE-PS 290 965), the diphenyl and ditolyl ether sulfonic acids (US Pat. No. 2,315,951) and terphenyl sulfonic acids (US Pat. No. 3,906,037) and their ammonium or alkali salts.
- So-called exchange tanning agents which are predominantly present as phenol-containing formaldehyde condensation products of aromatic sulfonic acids or their salts, are customary as retanning and / or leveling agents for chrome leather (GB-PS 1 291 784 and DT-PS 611 671).
- tanning agents and leveling agents There are gradual differences in the brightening effect on colorations between the different types of tanning agents and leveling agents, which may depend, among other things, on the ratio of leveling agents or retanning agents to dye and dye-specific, but they consistently cause high color loss on leather, which can reach 50 - 80% compared to leather that can be dyed under comparable conditions but without retanning or leveling agent treatment.
- the sulfonic acids or their salts of the formula (I), which have not been condensed to form larger molecules with formaldehyde like anionic synthetic tanning agents and leveling agents, are particularly suitable as retanning agents. They offer the advantage that the leather retanned with it or the leather treated before or during dyeing results in deep and brilliant surface dyeings with anionic dyes with excellent levelness. The color depth results similar to that of pure chrome leather, which does not come with after tannins and / or leveling agents have been treated.
- Suitable retanning agents of the formula (I), which allow a deep and brilliant coloration of the leather with optimal use of the dye range, are preferably suitable partially or completely with sodium hydroxide or - because of their better solubility - preferably mixtures of terphenyl-mono- and- neutralized with ammonia disulfonic acids. They can e.g. produce by allowing 2 mols of sulfuric acid monohydrate to act for 2 hours at 145-150 ° C. for 2 hours for sulfonation in accordance with US Pat. No. 3,906,037, Example 3, lines 44-54, for 1 mol of a technical terphenyl isomer mixture and then reacting the reaction mixture neutralizes the desired final pH and converts it into powder by spray drying.
- the technical isomer mixtures of terphenyl which are inevitably obtained as by-products in the diphenyl synthesis from benzene, are suitable and particularly economical as the starting product for the production of such terphenylsulfonic acid mixtures.
- the sulfonic acids and their salts of the formula (I) are optimally effective for levelness, brilliance and depth of the coloration of the leather, if they are mixed with anionic dyes in amounts of before or during the coloration 2 - 10%, preferably 3 - 6% (based on the so-called fold weight of the leather) act on the leather and let it open. They are particularly good at leveling the color and compensating for the different dyeability of damaged and undamaged areas within individual skins or skins if they are applied to the leather before the dye is added and the dye can then be evenly applied to the leveled leather.
- Chromium leather from cowhide or calfskin which is manufactured in the usual way, folded to 1.6 - 1.8 mm and neutralized to pH 3.8 - 4.2, is treated with 100% liquor in a rotating tanning drum with 6% of an acid number (mg KOH / g) 40 adjusted mixture of terphenyl mono- and di-sulfonic acid ammonium salts, which is formed when 2.4 mol of sulfuric acid monohydrate is allowed to act on a technical mixture of terphenyl isomers from the diphenyl synthesis at 150 ° C. in the course of 3 hours and then after cooling and diluting to acid number 40 neutralized with ammonia and spray dried.
- an acid number (mg KOH / g) 40 adjusted mixture of terphenyl mono- and di-sulfonic acid ammonium salts which is formed when 2.4 mol of sulfuric acid monohydrate is allowed to act on a technical mixture of terphenyl isomers from the diphenyl synthesis at 150
- dyeing is carried out in the customary manner with 1% of the copper complex of a monoazo dye from DE-PS 670 935, example 1.
- greasing is carried out in the dye bath in the customary manner and then treated with 1.5% formic acid in order to achieve the best possible absorption of the dye and the greasing.
- this leather corresponds to a leather dyed without auxiliary treatment with the same amount of dye, but which results in significantly lower levelness.
- a diphenyl ether disulfonic acid sodium salt for 10 minutes to initiate retanning in a 100% warm liquor.
- 2.4 mol of sulfuric acid monohydrate on 1 mol of diphenyl ether are advantageously allowed to act at 120 ° C. for 2 hours with vigorous stirring, the mixture is cooled, diluted, neutralized with sodium hydroxide solution and converted into powder form by spray drying.
- chrome leather which is folded and neutralized to pH 6.0 (cut color with bromotymol blue, yellow to yellow-green), is first washed with 300% water at 40 ° C in a customary manner. After draining the wash liquor, pre-greased with 2.5% of a sulfited leather-based grease agent based on trans in 100% of a liquor at 40 ° C. for 15 minutes and then in the same liquor for 10 minutes with 1% of an ammonia solution is that contains 2.5 percent by weight of NH 3 .
- o-Terphenyl-4,4 ', 4 "-trisulfonic acid is prepared by reacting 230 g each of o-terphenyl (approx. 95%) with 1500 g of sulfuric acid monohydrate at 110 ° C. for 90 minutes and with potassium chloride in the potassium salt transferred (see Journal of Organic Chemistry 14, 163 (1949)).
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792932688 DE2932688A1 (de) | 1979-08-11 | 1979-08-11 | Verfahren zum nachgerben mineralisch gegerbter leder mit aromatischen sulfonsaeuren |
| DE2932688 | 1979-08-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0024014A1 true EP0024014A1 (fr) | 1981-02-18 |
| EP0024014B1 EP0024014B1 (fr) | 1982-05-19 |
Family
ID=6078301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80104522A Expired EP0024014B1 (fr) | 1979-08-11 | 1980-07-31 | Procédé de retannage de cuirs tannés au minéral avec des acides sulfoniques aromatiques |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0024014B1 (fr) |
| JP (1) | JPS5628300A (fr) |
| AR (1) | AR220483A1 (fr) |
| BR (1) | BR8005016A (fr) |
| DE (2) | DE2932688A1 (fr) |
| ES (1) | ES8104420A1 (fr) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0347373A1 (fr) * | 1988-06-06 | 1989-12-20 | Ciba-Geigy Ag | Solutions aqueuses de tannins synthétiques |
| FR2658211A1 (fr) * | 1990-02-10 | 1991-08-16 | Sandoz Sa | Utilisation de composes aromatiques contenant des groupes sulfo, comme auxiliaires d'application dans la traitement des matieres fibreuses. |
| EP0470465A1 (fr) * | 1990-08-10 | 1992-02-12 | Bayer Ag | Procédé de retannage de cuir qui au préalable a subi un tannage minéral par des acides sulfoniques aromatiques |
| US6922431B1 (en) | 1997-07-31 | 2005-07-26 | Telefonaktiebolaget Lm Ericsson (Publ) | Communication using spread spectrum methods over optical fibers |
| WO2010130311A1 (fr) * | 2009-05-14 | 2010-11-18 | Clariant International Ltd | Procédé et composition de tannage |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5172228B2 (ja) | 2007-06-28 | 2013-03-27 | ミドリホクヨー株式会社 | 革 |
| MX2010012544A (es) | 2008-05-16 | 2011-03-15 | Midori Hokuyo Co Ltd | Recubrimiento superior. |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR505388A (fr) * | 1913-12-08 | 1920-07-29 | Basf Ag | Procédé de tannage, nouveaux produits tannants et leurs applications |
| US1945461A (en) * | 1930-12-10 | 1934-01-30 | Rohm & Haas | Method of retanning of chrome leather |
| US2292067A (en) * | 1941-04-25 | 1942-08-04 | Du Pont | Production of white leather |
| FR959065A (fr) * | 1950-03-23 | |||
| US2973240A (en) * | 1951-06-21 | 1961-02-28 | Boehme Fettchemie Gmbh | Tanning with alkylbenzene sulfonate in combination with chrome tanning |
| FR1282449A (fr) * | 1961-03-01 | 1962-01-19 | Stockhausen & Cie Chem Fab | Procédé d'égalisage des teintures sur cuirs ayant subi un tannage au chrome ou un tannage combiné |
| DE2048171A1 (de) * | 1969-09-30 | 1971-04-01 | Imperial Chemical Industries Ltd , London | Farbeverfahren |
| GB2006276A (en) * | 1977-09-24 | 1979-05-02 | Bayer Ag | Dyestuff formulations |
-
1979
- 1979-08-11 DE DE19792932688 patent/DE2932688A1/de not_active Withdrawn
-
1980
- 1980-07-31 DE DE8080104522T patent/DE3060449D1/de not_active Expired
- 1980-07-31 EP EP80104522A patent/EP0024014B1/fr not_active Expired
- 1980-08-07 JP JP10779880A patent/JPS5628300A/ja active Granted
- 1980-08-08 BR BR8005016A patent/BR8005016A/pt unknown
- 1980-08-08 ES ES494117A patent/ES8104420A1/es not_active Expired
- 1980-08-11 AR AR282118A patent/AR220483A1/es active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR959065A (fr) * | 1950-03-23 | |||
| FR505388A (fr) * | 1913-12-08 | 1920-07-29 | Basf Ag | Procédé de tannage, nouveaux produits tannants et leurs applications |
| US1945461A (en) * | 1930-12-10 | 1934-01-30 | Rohm & Haas | Method of retanning of chrome leather |
| US2292067A (en) * | 1941-04-25 | 1942-08-04 | Du Pont | Production of white leather |
| US2973240A (en) * | 1951-06-21 | 1961-02-28 | Boehme Fettchemie Gmbh | Tanning with alkylbenzene sulfonate in combination with chrome tanning |
| FR1282449A (fr) * | 1961-03-01 | 1962-01-19 | Stockhausen & Cie Chem Fab | Procédé d'égalisage des teintures sur cuirs ayant subi un tannage au chrome ou un tannage combiné |
| DE2048171A1 (de) * | 1969-09-30 | 1971-04-01 | Imperial Chemical Industries Ltd , London | Farbeverfahren |
| GB2006276A (en) * | 1977-09-24 | 1979-05-02 | Bayer Ag | Dyestuff formulations |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0347373A1 (fr) * | 1988-06-06 | 1989-12-20 | Ciba-Geigy Ag | Solutions aqueuses de tannins synthétiques |
| FR2658211A1 (fr) * | 1990-02-10 | 1991-08-16 | Sandoz Sa | Utilisation de composes aromatiques contenant des groupes sulfo, comme auxiliaires d'application dans la traitement des matieres fibreuses. |
| BE1005672A3 (fr) * | 1990-02-10 | 1993-12-14 | Sandoz Sa | Utilisation de composes aromatiques contenant des groupes sulfo, comme auxiliares d'application dans le traitement des matieres fibreuses. |
| EP0470465A1 (fr) * | 1990-08-10 | 1992-02-12 | Bayer Ag | Procédé de retannage de cuir qui au préalable a subi un tannage minéral par des acides sulfoniques aromatiques |
| US5352241A (en) * | 1990-08-10 | 1994-10-04 | Bayer Aktiengesellschaft | Process for retanning mineral tanned leathers with aromatic sulphonic acids |
| US6922431B1 (en) | 1997-07-31 | 2005-07-26 | Telefonaktiebolaget Lm Ericsson (Publ) | Communication using spread spectrum methods over optical fibers |
| WO2010130311A1 (fr) * | 2009-05-14 | 2010-11-18 | Clariant International Ltd | Procédé et composition de tannage |
| CN102282269A (zh) * | 2009-05-14 | 2011-12-14 | 科莱恩金融(Bvi)有限公司 | 鞣制方法和鞣制组合物 |
| US8679195B2 (en) | 2009-05-14 | 2014-03-25 | Clariant Finance (Bvi) Limited | Tanning process and tanning composition |
| CN102282269B (zh) * | 2009-05-14 | 2014-10-29 | 克拉里安特国际有限公司 | 鞣制方法和鞣制组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| AR220483A1 (es) | 1980-10-31 |
| DE3060449D1 (en) | 1982-07-08 |
| JPS6318640B2 (fr) | 1988-04-19 |
| JPS5628300A (en) | 1981-03-19 |
| ES494117A0 (es) | 1981-03-16 |
| ES8104420A1 (es) | 1981-03-16 |
| BR8005016A (pt) | 1981-02-24 |
| DE2932688A1 (de) | 1981-02-26 |
| EP0024014B1 (fr) | 1982-05-19 |
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