CN101978077A - Method for manufacturing leather - Google Patents
Method for manufacturing leather Download PDFInfo
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- CN101978077A CN101978077A CN2009801100165A CN200980110016A CN101978077A CN 101978077 A CN101978077 A CN 101978077A CN 2009801100165 A CN2009801100165 A CN 2009801100165A CN 200980110016 A CN200980110016 A CN 200980110016A CN 101978077 A CN101978077 A CN 101978077A
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- Prior art keywords
- acid
- alkali metal
- mixture
- poly carboxylic
- leather
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000010985 leather Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 75
- -1 alkali metal salts Chemical class 0.000 claims abstract description 44
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 59
- 239000000203 mixture Substances 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 150000003863 ammonium salts Chemical class 0.000 claims description 21
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 14
- 150000001735 carboxylic acids Chemical class 0.000 claims description 11
- 235000013311 vegetables Nutrition 0.000 claims description 9
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 3
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 abstract 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 abstract 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 18
- 239000002253 acid Substances 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 9
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 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 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 7
- 229940009662 edetate Drugs 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 241000675108 Citrus tangerina Species 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- 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 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000003818 basic metals Chemical class 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000012256 powdered iron Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical group OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 101100117236 Drosophila melanogaster speck gene Proteins 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 235000017343 Quebracho blanco Nutrition 0.000 description 2
- 241000065615 Schinopsis balansae Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- 210000000051 wattle Anatomy 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KHTDNUMAGDXZNW-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C12CCC(CC1)C2 Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C12CCC(CC1)C2 KHTDNUMAGDXZNW-UHFFFAOYSA-N 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 241000282898 Sus scrofa Species 0.000 description 1
- NSIKFNOYIGGILA-UHFFFAOYSA-N [Na].[Na].[K] Chemical compound [Na].[Na].[K] NSIKFNOYIGGILA-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GGAUUQHSCNMCAU-UHFFFAOYSA-N butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(C(O)=O)CC(O)=O GGAUUQHSCNMCAU-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
- C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/10—Vegetable tanning
-
- 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
Abstract
The present invention relates to a method for manufacturing leather, characterized in that the pre-tanning, main-tanning or post-tanning is carried out in the presence of (a) at least one compound of the general formula (I) (b) and oxalic acid or the corresponding ammonium or alkali metal salts thereof, respectively, where R1 is selected from methyl, ethyl, phenyl, benzyl, hydroxymethyl, isopropyl, isobutyl and sec.-butyl.
Description
The present invention relates to the production method of leather, wherein pretan, the master tans or retanning is carried out in the presence of following compounds:
(a) at least a compound of Formula I:
With
(b) oxalic acid
Or corresponding ammonium salt or an alkali metal salt under every kind of situation,
R wherein
1Be selected from methyl, ethyl, phenyl, benzyl, methylol, sec.-propyl, isobutyl-and sec-butyl.
The invention further relates to the mixture of following compounds:
(a) at least a compound of Formula I and
(b) oxalic acid,
(c) if suitable, alkali metal formate, and
(d) if suitable, at least a dicarboxylic acid or poly carboxylic acid
Or corresponding ammonium salt or an alkali metal salt under every kind of situation.
In many application, need light-colored leather.Especially when needs light tone leather, black, brown or lead spot are undesirable.Yet in conventional process for tanning, the undesirable spot of this class is all observed in many cases.
Black, formation brown or the lead spot are owing to iron cpd, especially ferriferous oxide and ironic hydroxide in many cases, Fe
2O
3Solution and because the typical iron blackening (iron speck) of use vegetable tanning agent.If for example small pieces break away from and are dissolved in the moisture owse and form iron cpd, then form this class spot from the cutter of shaving machine with rotation steel knife or other metal assemblies.Then in and the time, ferric oxide and/or ironic hydroxide may be deposited on the leather.
The blackening problem is especially serious when using vegetable tanning agent.Usually vegetable tanning agent comprises tangerine acid or tangerine hydrochlorate.Tangerine acid and iron form complex compound and it has aterrimus and just known as ink composition from Middle Ages.For producing light-colored leather, in tanning and retanning, should avoid the existence of tangerine acid printing ink.
For forming iron cpd in process for tanning, prevention made many trials.Steel seems indispensable in the production of shaving machine.Therefore attempt by sheltering (chelating, complexing) thus stop the dissolved deposition of iron on leather.Yet traditional part is accompanied by shortcoming.
Is successful at iron really with the trial of iron and edetate (EDTA) complexing aspect sheltering.Yet therefore EDTA can make heavy metal move to the water body from slurry is undesirable in waste water also.In addition, EDTA is difficult for degraded and COD (chemical oxygen demand (COD)) height.
Therefore purpose provides a kind of method of eliminating known disadvantage and the production leather of immaculate leather being provided.Further purpose provides material or the substance mixture that can produce the immaculate leather.
Therefore, found the method that begins to define, it is also referred to as the inventive method hereinafter.
The inventive method is the method for a kind of pretan, main tan (also comprising tanning) or retanning; The inventive method is preferably the retanning method.
The inventive method is from the pre-treatment rawhide of dead animal such as ox, pig, goat or deer.Animal whether be for example by butcher or kill by going hunting or because of natural cause death inessential to the inventive method.Conventional pretreatment process for example comprises liming, deliming, softening and dipping and power operation such as rawhide fleshing and especially shaving.
In embodiments of the invention, the inventive method is carried out as the retanning method.For this reason, with tanned animal hides, so-called work in-process as raw material, wherein can carry out tanning with any required known tanning agent own such as compound, Polymer Tanning Agent, aldehyde tanning agent, vegetable tanning agent or the synthetic tanning agent of Cr (III).Therefore used work in-process can be wet blue leather (wet blue) or white wet leather (wet white).
The inventive method is carried out in aqueous fluid.Suitable bath raio for example can be 50-250%.
In addition, the inventive method is carried out in the presence of following compounds:
(a) at least a compound of Formula I:
(b) oxalic acid
Or corresponding ammonium salt or an alkali metal salt under every kind of situation, wherein basic metal is selected from lithium, rubidium, caesium, preferred potassium and especially preferred sodium, and
R wherein
1Be selected from methyl, ethyl, phenyl, benzyl, methylol, sec.-propyl, isobutyl-and sec-butyl.R
1Be preferably selected from methyl and methylol, especially methyl.
Nitrogen-atoms in the compound of Formula I can be unprotonated or protonated.
The corresponding ammonium salt of compound of Formula I or an alkali metal salt can be regarded as mono-ammonium, di-ammonium salts and three ammonium salts or single an alkali metal salt, two an alkali metal salts and three an alkali metal salts that are meant compound of Formula I, mixing salt is also included within the situation of two an alkali metal salts and three an alkali metal salts, for example single sodium monopotassium salt, disodium monopotassium salt and single sodium mono-ammonium.
Compound of Formula I can be used as that racemoid exists or exists with a kind of form of or other enantiomorphs.
The preparation of compound of Formula I is own known and is for example undertaken by amino acid whose carboxymethylation.
In addition, use oxalic acid (b) or corresponding ammonium salt or an alkali metal salt in the inventive method.The corresponding ammonium salt of oxalic acid or an alkali metal salt can be regarded as mono-ammonium and di-ammonium salts and single an alkali metal salt and two an alkali metal salts that are meant oxalic acid respectively, and mixing salt is also included within the situation of two an alkali metal salts, for example oxalic acid list sodium monopotassium salt and oxalic acid list sodium mono-ammonium.
In embodiments of the invention, the inventive method is additionally carried out in the presence of following compounds:
(c) at least a alkali metal formate,
Wherein basic metal is selected from lithium, rubidium, caesium, preferred potassium and especially preferred sodium,
Or in the presence of formic acid, carry out as corresponding free acid.Also be included in the method under formic acid/formate damping fluid existence.
In embodiments of the invention, the inventive method is additionally carried out in the presence of following compounds:
(d) at least a dicarboxylic acid or poly carboxylic acid
Or corresponding ammonium salt or an alkali metal salt under every kind of situation, wherein basic metal is selected from lithium, rubidium, caesium, preferred potassium and especially preferred sodium.
Be similar to compound of Formula I, also comprise blended two an alkali metal salts or polyacid base metal-salt, and comprise because in the part and dicarboxylic acid or poly carboxylic acid (d) those ammonium salts and an alkali metal salt that obtain.
Dicarboxylic acid (d) is different with oxalic acid.For example, dicarboxylic acid (d) can be C
3-C
12Dicarboxylic acid.
Dicarboxylic acid (d) can have straight chain or branching carbochain and can be cyclic or preferred acyclic.Dicarboxylic acid (d) can have aromatic ring or alicyclic ring, and dicarboxylic acid (d) can have dicyclo or encircle carbon skeleton more.Dicarboxylic acid (d) can have one or more ethylenic unsaturated double-bonds.The example of suitable dicarboxylic acids (d) is phthalic acid, terephthalic acid, m-phthalic acid, toxilic acid, fumaric acid, methylene-succinic acid, cyclohexane cyclohexanedimethanodibasic (the especially 1,4 cyclohexanedicarboxylic acid of isomery), norbornane dioctyl phthalate and norbornylene dioctyl phthalate.
Yet dicarboxylic acid (d) comprises preferably that one or more are unsubstituted or replaced or polysubstituted aliphatic dicarboxylic acid by the hydroxyl list.In the variant of the present invention, dicarboxylic acid (d) is monohydroxy dicarboxylic acid or dihydroxyl dicarboxylic acid.Especially suitable aliphatic dicarboxylic acid example is tartrate, oxysuccinic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, sebacic acid and pimelic acid; The binary and the tertiary mixture of preferred tartrate, succsinic acid, pentanedioic acid and hexanodioic acid and succsinic acid, pentanedioic acid and hexanodioic acid.
Poly carboxylic acid (d) can have straight chain or branching carbochain.Poly carboxylic acid (d) is preferably the compound that per molecule has 3-5 carboxyl; The aliphatic polycarboxylic acid is especially preferably unsubstituted or replaced by the hydroxyl list or polysubstituted.Preferred butane-1,2,3,4-tetracarboxylic acid and optimization citric acid especially.
In embodiments of the invention, the inventive method is additionally carried out in the presence of xitix (e).Also be included in the method under the existence of xitix ammonium or one or more basic metal ascorbate salts.Xitix can be used as that racemoid exists or with a kind of form of its enantiomorph, especially exists as (L)-xitix.
In embodiments of the invention, the inventive method is carried out in the presence of following compounds:
0.01-1 weight %, the compound of Formula I of preferred 0.03-0.25 weight %,
0.005-0.75 weight %, the oxalic acid (b) of preferred 0.02-0.125 weight %,
If suitable, 0.001-4 weight %, the alkali metal formate (c) of preferred 0.02-2 weight %,
If suitable, be total up to 0.001-0.75 weight %, dicarboxylic acid or the poly carboxylic acid (d) of preferred 0.03-0.175 weight %,
If suitable, 0.001-0.3 weight %, the xitix of preferred 0.05 weight % (e),
Wherein in the data of weight % weight based on shaving.
The inventive method is for example carried out as follows: with at least a compound of Formula I and oxalic acid (b), if the mixture of suitable conduct and alkali metal formate (c), dicarboxylic acid or poly carboxylic acid (d) or xitix (e) once or several times adds before being close to the tanning step or among the tanning step.The inventive method is preferably carried out under pH 2.5-4 then, and when carrying out the inventive method, often observing pH increases about 0.3-3 unit.Also can make pH increase about 0.3-3 unit by adding basifier.
The inventive method is 10-45 ℃ in temperature usually, carries out under preferred 20-30 ℃.10 minutes to 12 hours time length proves useful, and preferred 3 hours time length at the most.Carry out in any required container that the inventive method can be used always in tanning, for example by in bucket or in having the rotary drum of internals, overturning.
In the variant of the inventive method with at least a compound of Formula I and oxalic acid (b), if suitable conduct and alkali metal formate (c), the mixture of dicarboxylic acid or poly carboxylic acid (d) or xitix (e), with one or more conventional tanning agent such as chrome tanning agent, mineral tanning agent, synthetic tanning agent, Polymer Tanning Agent or especially vegetable tanning agent use together, for example as Ullmann ' s Encyclopedia of IndustrialChemistry, the A15 volume, the 259-282 page or leaf and especially the 268th page and below, the 5th edition (1990) are described in the Verlag Chemie Weinheim.Particularly preferred vegetable tanning agent is quebracho extract and wattle.
In the variant of the inventive method, with at least a compound of Formula I and oxalic acid (b), if the mixture of suitable conduct and alkali metal formate (c), dicarboxylic acid or poly carboxylic acid (d) or xitix (e), before the pretan or among add once or several times, in special variant, add in the pickling liquid (pickle) itself.
In the further variant of the inventive method, with at least a compound of Formula I and oxalic acid (b), if the mixture of suitable conduct and alkali metal formate (c), dicarboxylic acid or poly carboxylic acid (d) or xitix (e), before the retanning step or among once or several times add.This variant is also referred to as retanning method of the present invention hereinafter.Retanning method of the present invention is from the rawhide of pretan.
Retanning method of the present invention can be carried out under the conventional in other respects condition.Advantageously select one or morely to soak step and soaking between the step and can wash as 2-6.The temperature of respectively soaking in the step is 5-60 ℃ in each case, preferred 20-45 ℃.Can use one or more other compositions commonly used in retanning, fat liquor for example, one or more conventional retanning agents such as chrome tanning agent, mineral tanning agent, synthetic tanning agent, Polymer Tanning Agent or especially vegetable tanning agent also have leather dyestuff in addition, increase composition or the emulsifying agent of pH.
In variant of the present invention, in tanning, pretan or retanning, add at least a compound of Formula I and oxalic acid (b) respectively, if appropriate base metal formate (c), dicarboxylic acid or poly carboxylic acid (d) or xitix (e).
By the inventive method, if obtained to have the immaculate leather of superior mechanical properties-be suitably in by after the traditional method aftertreatment.In addition, the waste water of acquisition usually aftertreatment easily and its chemistry and biological oxygen demand not because of compound of Formula I and the improper increase of oxalic acid (b) (if suitable) with alkali metal formate (c), dicarboxylic acid or poly carboxylic acid (d) or xitix (e).
The invention further relates to the mixture that comprises following compounds:
(a) at least a compound of Formula I:
(b) oxalic acid
Or corresponding ammonium salt or an alkali metal salt under every kind of situation,
R wherein
1Be selected from methyl, ethyl, phenyl, benzyl, methylol, sec.-propyl, isobutyl-and sec-butyl.
R
1Be preferably selected from methyl and methylol, especially methyl.
Nitrogen-atoms in the compound of Formula I can be unprotonated or protonated.
In embodiments of the invention, mixture of the present invention additionally comprises:
(c) alkali metal formate.
In embodiments of the invention, mixture of the present invention additionally comprises:
(d) at least a dicarboxylic acid or poly carboxylic acid
Or corresponding ammonium salt or an alkali metal salt.
In embodiments of the invention, poly carboxylic acid (d) is tricarboxylic acid or tetracarboxylic acid or corresponding ammonium salt or an alkali metal salt.
In embodiments of the invention, dicarboxylic acid or poly carboxylic acid are monohydroxy-or dihydroxyl dicarboxylic acid or monohydroxy-or dihydroxyl poly carboxylic acids.
Above-mentioned explanation is applicable to corresponding ammonium salt or the corresponding ammonium salt of an alkali metal salt, dicarboxylic acid or poly carboxylic acid (d) or the corresponding ammonium salt or an alkali metal salt of an alkali metal salt and oxalic acid (b) of compound of Formula I.
In embodiments of the invention, mixture of the present invention additionally comprises:
(e) xitix.
In embodiments of the invention, mixture of the present invention can further comprise water.
In other embodiments of the present invention, mixture of the present invention also can comprise salt such as the sodium sulfate that improves flowability.For example, mixture of the present invention can comprise the salt of 5-30 weight %, especially sodium sulfate.
In embodiments of the invention, mixture of the present invention comprises:
10-60 weight %, the compound of Formula I of preferred 15-50 weight %,
5-50 weight %, the oxalic acid (b) of preferred 10-25 weight %,
If suitable, 1-50 weight %, the alkali metal formate (c) of preferred 10-30 weight %,
If suitable, be total up to 1-50 weight %, dicarboxylic acid or the poly carboxylic acid (d) of preferred 15-35 weight %,
If suitable, 1-20 weight %, the xitix (e) of preferred 2.5-10 weight %,
Wherein in the data of weight % based on total mixture of the present invention.
Mixture of the present invention especially is fit to carry out the inventive method.The invention further relates to the purposes of mixture of the present invention in carrying out the inventive method.The invention further relates to a kind of method of using at least a mixture production leather of the present invention.
In embodiments, use 0.1-1.5 weight % based on shaving weight, the mixture of the present invention of preferred 0.2-0.5 weight % carries out the inventive method.
Mixture of the present invention can be by known method preparation itself, especially pass through compound of Formula I and oxalic acid (b), if appropriate base metal formate (c) if suitable at least a dicarboxylic acid or poly carboxylic acid (d) and if suitable xitix (e) mix, especially by stirring.
The present invention is by work embodiment explanation.
I. prepare mixture of the present invention
Component in the table 1 is mixed in stirred vessel and has been obtained mixture M .2-M.5 of the present invention and control mixture C-M.1.
The composition of table 2 mixture M .2-M.5 of the present invention and control mixture C-M.1
| Mixture | (a.1) | ?(b) | (c.1) | (d.1) | (d.2) | ?(e) |
| C-M.1 | 60 | - | - | 25 | 15 | - |
| M.2 | 50 | 50 | - | - | - | - |
| M.3 | 35 | 15 | 30 | 10 | 15 | 5 |
| M.4 | 40 | 25 | - | 15 | 15 | 5 |
| M.5 | 30 | 20 | 20 | 10 | 20 | - |
Illustrate:
(a.1)：
(c.1): sodium formiate
(d.1): C
4-C
6The dicarboxylic acid mixture, the mixture of succsinic acid, pentanedioic acid, hexanodioic acid, weight ratio is 1: 1: 3.
(d.2): citric acid
(b): formic acid; (e): (L)-xitix
Data are in weight % under every kind of situation.
II. the use in the retanning/method of the present invention of producing leather of mixture of the present invention and control mixture
Unless have other to express explanation, be based on the amount of shaving weight and expression active substance under every kind of situation in the data of weight %.
Do not use dyestuff in an embodiment, thereby can more easily measure the formation of spot.In addition, add the powdered iron particle.Yet embodiment also can use one or more leather dyestuffs and omit under the described processing of powdered iron particulate and carry out.
(be abbreviated as wb, the cow hide (being abbreviated as ww) that US-Packer) and in vain wets is cut 1.8mm and is switched to the central zone with the wet cow hide of indigo plant.After this, its branch is put in two rotary drums that separate.Then by allowing 0.7 weight % sodium formiate and 0.2 weight %NaHCO
3Upset was worked and is neutralized in 60 minutes under the bath raio of 20 ℃ and 100 weight % water.When processing finished, recording pH was 4.8-5.0.After this, work in-process are washed twice, at every turn with 10 (wb and ww) being cut under the water of 100 weight % and the every kind of situation separately to about 400g.This moment is with 0.5g/dm
3Powdered iron particle (mean diameter 50 μ m) evenly spray on the work in-process bar.With plastic plate the work in-process bar is covered then and on pallet, placed 8 hours.Then the work in-process bar is distributed in 20 rotary drums that separate, with the water treatment of 60 weight % and add the sulfone tanning agent of 6 weight %EP-B, 0 459 168 embodiment K1.30 ℃ of down upsets after 20 minutes, being metered into 0.9 weight % sodium formiate step of going forward side by side carries out 30 minutes upset (30 ℃).After this, add mixture of the present invention or control mixture or complexing agent that 0.3 weight % lists in table 1, add the fat liquor (based on sulfited fish oil) of 1 weight %WO, 03/023069 embodiment A subsequently.After upset 15 minutes, be metered into vegetable tanning agent wattle and the quebracho of 6 weight % respectively.After further overturning 40 minutes, be metered into the fat liquor of 3 weight %WO, 03/023069 embodiment A.Further carry out 20 minutes upset and add 2 weight % then, the naphthene sulfonic acid/formaldehyde condensation products of 186,846 embodiment " dispersion agent 1 " preparation according to US5.Further carry out 120 minutes upset.Then liquid is discharged.
After liquid is discharged, the leather piece that obtains is washed twice, use the water of 100 weight % at every turn.The leather piece that is covered by plate stores at least 6 hours on pallet.After the sclerosis, will remove from office piece then 60-70 ℃ of following drying under reduced pressure 4 minutes.In surge chamber or by being positioned in the moist wood shavings, regulate 12 hours down before the visually rank in 40 ℃.
L.11, having obtained contrast leather C-L.1 L.20 arrives to C-L.10 and leather produced according to the invention.
The results are shown in Table 1 for visually rank.
Leather of the present invention and contrast leather are according to the mark system assessment of 1-5.Here, mark 1 expression based on the no variable color of chromatic number (wet blue leather or white wet leather), and so does not have iron speck and inhomogeneous at leather in appearance except that the crust leather true qualities.Mark 5 corresponding greyish black leathers.
Table 2: L.11 contrast leather C-L.1 arrives L.20 result of study to C-L.10 and leather produced according to the invention
| Embodiment/leather | Tanning | Complexing agent | Chromatic number | Spot/uniformity coefficient |
| C-L.1 | Wet blue leather | - | 5 | 5 |
| C-L.2 | White wet leather | - | 5 | 5 |
| C-L.3 | Wet blue leather | EDTA | 3 | 2 |
| C-L.4 | White wet leather | EDTA | 1.5 | 2 |
| C-L.5 | Wet blue leather | Oxalic acid | 3 | 2.5 |
| C-L.6 | White wet leather | Oxalic acid | 3 | 2.5 |
| C-L.7 | Wet blue leather | (a.1) | 2.5 | 3 |
| C-L.8 | White wet leather | (a.1) | 3.5 | 3 |
| C-L.9 | Wet blue leather | C-M.1 | 4 | 3 |
| C-L.10 | White wet leather | C-M.1 | 3 | 3 |
| L.11 | Wet blue leather | M.2 | 2 | 2 |
| L.12 | White wet leather | M.2 | 2 | 2 |
| L.13 | Wet blue leather | M.3 | 1 | 1 |
| L.14 | White wet leather | M.3 | 2 | 1.5 |
| L.15 | Wet blue leather | M.4 | 2 | 2 |
| L.18 | White wet leather | M.4 | 2 | 2 |
| L.19 | Wet blue leather | M.5 | 2 | 2 |
| L.20 | White wet leather | M.5 | 2.5 | 2 |
The waste water that forms in the production of C-L.3 and C-L.4 has extremely disadvantageous COD (chemical oxygen demand (COD)) and comprises the EDTA that does not consume.
Claims (14)
1. method of producing leather, wherein pretan, the master tans or retanning is carried out in aqueous fluid in the presence of following compounds:
(a) at least a compound of Formula I:
(b) oxalic acid
Or corresponding ammonium salt or an alkali metal salt under every kind of situation,
R wherein
1Be selected from methyl, ethyl, phenyl, benzyl, methylol, sec.-propyl, isobutyl-and sec-butyl.
2. according to the method for claim 1, it additionally carries out in the presence of following compounds:
(c) alkali metal formate.
3. according to the method for claim 1 or 2, it additionally carries out in the presence of following compounds:
(d) at least a dicarboxylic acid or poly carboxylic acid
Or corresponding ammonium salt or an alkali metal salt under every kind of situation.
4. according to each method of claim 1-3, wherein poly carboxylic acid (d) is tricarboxylic acid or tetracarboxylic acid or corresponding ammonium salt or an alkali metal salt.
5. according to each method of claim 1-4, wherein dicarboxylic acid or poly carboxylic acid are monohydroxy-or dihydroxyl dicarboxylic acid or monohydroxy-or dihydroxyl poly carboxylic acids.
6. according to each method of claim 1-5, it additionally carries out in the presence of following compounds:
(e) xitix.
7. according to each method of claim 1-6, it carries out in the presence of at least a vegetable tanning agent.
8. mixture, it comprises:
(a) at least a compound of Formula I:
(b) oxalic acid
Or corresponding ammonium salt or an alkali metal salt under every kind of situation,
R wherein
1Be selected from methyl, ethyl, phenyl, benzyl, methylol, sec.-propyl, isobutyl-and sec-butyl.
9. mixture according to Claim 8, it additionally comprises:
(c) alkali metal formate.
10. want 8 or 9 mixture according to right, it additionally comprises:
(d) at least a dicarboxylic acid or poly carboxylic acid
Or corresponding ammonium salt or an alkali metal salt.
11. each mixture according to Claim 8-10, wherein poly carboxylic acid (d) is tricarboxylic acid or tetracarboxylic acid or corresponding ammonium salt or an alkali metal salt.
12. each mixture according to Claim 8-11, wherein dicarboxylic acid or poly carboxylic acid are monohydroxy-or dihydroxyl dicarboxylic acid or monohydroxy-or dihydroxyl poly carboxylic acids.
13. each mixture according to Claim 8-12, it additionally comprises:
(e) xitix.
14. each mixture is according to the purposes in each the method for claim 1-7 according to Claim 8-13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08153056 | 2008-03-20 | ||
| EP08153056.0 | 2008-03-20 | ||
| PCT/EP2009/053071 WO2009115487A1 (en) | 2008-03-20 | 2009-03-16 | Method for manufacturing leather |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101978077A true CN101978077A (en) | 2011-02-16 |
Family
ID=40932073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801100165A Pending CN101978077A (en) | 2008-03-20 | 2009-03-16 | Method for manufacturing leather |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2257650A1 (en) |
| CN (1) | CN101978077A (en) |
| BR (1) | BRPI0909178A2 (en) |
| WO (1) | WO2009115487A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113227407A (en) * | 2018-12-21 | 2021-08-06 | 朗盛德国有限责任公司 | Leather assistant for preparation before tanning |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855286A (en) * | 1971-10-01 | 1974-12-17 | Ciba Geigy Corp | N-carboxymethyl-n-(2-hydroxybenzyl) aspartic acid and derivatives thereof |
| CN1312387A (en) * | 2001-03-23 | 2001-09-12 | 山东省博兴县立鑫皮艺有限公司 | Production process of ox and hourse fur and leather |
| CN101050308A (en) * | 2007-04-29 | 2007-10-10 | 温州大学 | Method for preparing new type leather from disused leather |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB590834A (en) * | 1945-01-13 | 1947-07-30 | Richard Hodgson And Sons Ltd | Improvements in and relating to vegetable-tanned leathers |
| DE2061898A1 (en) * | 1969-12-17 | 1971-06-24 | W R Grace & Co , Cambridge, Mass (V St A) | Tanning agents |
| CH647259A5 (en) * | 1980-04-29 | 1985-01-15 | Sandoz Ag | METHOD FOR TANNING ANIMAL SKIN AND SKIN WITH IRON SALT. |
-
2009
- 2009-03-16 CN CN2009801100165A patent/CN101978077A/en active Pending
- 2009-03-16 WO PCT/EP2009/053071 patent/WO2009115487A1/en active Application Filing
- 2009-03-16 EP EP09722872A patent/EP2257650A1/en not_active Withdrawn
- 2009-03-16 BR BRPI0909178-5A patent/BRPI0909178A2/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855286A (en) * | 1971-10-01 | 1974-12-17 | Ciba Geigy Corp | N-carboxymethyl-n-(2-hydroxybenzyl) aspartic acid and derivatives thereof |
| CN1312387A (en) * | 2001-03-23 | 2001-09-12 | 山东省博兴县立鑫皮艺有限公司 | Production process of ox and hourse fur and leather |
| CN101050308A (en) * | 2007-04-29 | 2007-10-10 | 温州大学 | Method for preparing new type leather from disused leather |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113227407A (en) * | 2018-12-21 | 2021-08-06 | 朗盛德国有限责任公司 | Leather assistant for preparation before tanning |
| CN113227407B (en) * | 2018-12-21 | 2023-08-11 | 德瑞皮革科技有限公司 | Preparation of leather auxiliary before tanning |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0909178A2 (en) | 2015-08-25 |
| WO2009115487A1 (en) | 2009-09-24 |
| EP2257650A1 (en) | 2010-12-08 |
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