CN1109509A - Method of improving leather treatment - Google Patents
Method of improving leather treatment Download PDFInfo
- Publication number
- CN1109509A CN1109509A CN 94116442 CN94116442A CN1109509A CN 1109509 A CN1109509 A CN 1109509A CN 94116442 CN94116442 CN 94116442 CN 94116442 A CN94116442 A CN 94116442A CN 1109509 A CN1109509 A CN 1109509A
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- China
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- weight
- acid
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- multipolymer
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Classifications
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- 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
- C14C3/22—Chemical tanning by organic agents using polymerisation products
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
A method of using a dispersion of a selected amphiphilic copolymer formed from a predominant amount of at least one hydrophobic monomer and a minor amount of at least one copolymerizable hydrophilic monomer in the pretanning and tanning step improves moisture release in the wringing step and improves thickness adjustment in the splitting and shaving steps of leather treatment is disclosed.
Description
The present invention relates to a kind of method of improving leather processing, more particularly, relate to and use selected polymkeric substance to improve the extruding of leather in handling, isolate and finishing process.
Rawhide of animal and epidermis are transformed into useful leather by processing.This processing comprises hygrometric state treatment process and anhydrous treatment process.The hygrometric state treatment process comprises deburring, arrangement, dipping, fleshing, unhairing, softening, acidleach, tanning, pushes, isolates, finishing, retanning, dyeing, emulsion oil-filling and open and flat.In some this type of operation, rawhide or epidermis are placed under the felicity condition carrying out the following process operation, and other these type of operations make the performance of rawhide or epidermis or outward appearance that bigger variation take place.Other operations in this processing in each operation and one or more should the processing are interrelated.
Usually, leather be by at first by acidleach, made by tanning and neutral rawhide then.The raw hide of tanning is with after wherein residual moisture is removed in extruding, so that this raw hide isolating and repairing on the machinery and suitably handle, thereby the thickness of the raw hide of this tanning adjusted to the requirement that meets end-use.
Chromic salts usually is used for the tanning rawhide, because can make stable rawhide like this.Yet when the chrome tanning leather is isolated and repairs subsequently, produced the remaining waste liquid that contains some chromic salts.Some tanyards are just managing to finish that machinery isolates and finishing operation before rawhide carries out chrome tanning, so that remaining waste liquid does not contain chromic salts at all.These tanyards have run into a difficult problem in this respect, because be to have viscosity without the characteristics of the rawhide of chrome tanning, thereby on the processor that makes rawhide adhere to be used for isolating and repairing.Our invention overcomes this sticking problem when making tanyard isolate and to repair before chrome tanning.In addition, though isolate with finishing process before carry out this operation of chrome tanning, our invention also can improve and isolate and finishing process.
We find, use the dispersion of a certain selected amphipathic multipolymer to improve the moisture in the extrusion process in pretan and tanning operation and discharge, improved also that leather handles isolate with finishing process in the thickness adjustment.Above-mentioned amphipathic multipolymer is formed by at least a hydrophobic monomer that accounts for main amount and more a spot of at least a wetting ability copolymerisable monomer.
A kind of method of the present invention is included in the dispersion of also using a certain selected amphipathic multipolymer in pretan and the tanning operation except using other pretan and tanning agents.This amphipathic multipolymer is formed by at least a hydrophobic monomer that accounts for main amount and more a spot of at least a wetting ability copolymerisable monomer.The moisture of the tan leather that obtains in extrusion process discharges and to be improved, and also is improved in isolating of handling of leather and thickness adjustment in the finishing process.
Above-mentioned selected amphipathic multipolymer must contain at least a hydrophobic group because of and at least a hydrophilic group because of.This multipolymer is by greater than 10%(weight) to less than 50%(weight) at least a hydrophilic monomer and greater than 50%(weight) to less than 90%(weight) at least a hydrophobic comonomer form.Preferably this multipolymer is by greater than about 15%(weight) to less than about 45%(weight) at least a hydrophilic monomer and greater than about 55%(weight) to less than about 85%(weight) at least a hydrophobic comonomer form, and more preferably this multipolymer by greater than about 20%(weight) extremely less than about 40%(weight) and at least a hydrophilic monomer and greater than about 60%(weight) extremely less than about 80%(weight) at least a hydrophobic comonomer form.
The hydrophilic monomer that is used for preparing amphipathic multipolymer is that to be selected from water-soluble olefinic undersaturated at least, and preferred monoene belongs to a kind of monomer of undersaturated acidity or alkaline monomer or its mixture.The example of suitable hydrophilic monomer comprises vinylformic acid; Methacrylic acid; Methylene-succinic acid; Fumaric acid; Toxilic acid; And this type of sour acid anhydride; (methyl) acrylate that acid replaces, for example, methacrylic acid etherophosphoric acid and methacrylic ester sulfo group ethyl ester; (methyl) acrylamide that acid replaces, for example, 2-acrylamido-2-methyl-propyl sulfonic acid; With replacement (methyl) the vinylformic acid pattern of alkalescence and (methyl) acrylamide, for example, comprise methacrylic ester that the amine of dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate replaces and dimethylamino-propyl Methacrylamide etc.The water-soluble hydrophilic monomer that preferably is used to prepare two hydrophilic copolymers is vinylformic acid and methacrylic acid.
To the kind of hydrophilic monomer and the selection of concentration amphipathic multipolymer is scattered in the external phase (as water) well, simultaneously can operate the amphipathic multipolymer of viscosity high polymers amount of solid ground preparation that maybe can shear, and can the ability that multipolymer infiltrates leather not had a negative impact with a certain.
The hydrophobic comonomer that is used for preparing amphipathic multipolymer is to be selected from following a kind of monomer at least: (methyl) alkyl acrylate, and elementary alkene and alkyl carboxylic acid vinyl acetate, with and composition thereof.Suitable hydrophobic monomer comprises vinylformic acid C
4-C
12Alkyl ester, methacrylic acid C
4-C
12Alkyl ester; C
4-C
121-alkene, and C
4-C
12The vinyl acetate of alkyl carboxylic acid.We find that the hydrophobic monomer that can offer the best performance characteristic for amphipathic multipolymer is preferably (methyl) vinylformic acid C
4-C
12Alkyl ester and its mixture, most preferably 2-EHA.
Used in this article term " (methyl) " and term such as acrylate or acrylamide logotype refer to acrylate or acrylamide respectively, methacrylic ester and Methacrylamide.
But the ethylenically unsaturated monomer of more a spot of other copolymerization can be to be equal to or less than the 50%(weight of hydrophobic comonomer total concn) concentration and a certain main amount (greater than about 50%(weight) that accounts for) at least a above type hydrophobic comonomer and use.These extra hydrophobic comonomers can be used as the thinner of other hydrophobic comonomers, and can not have a negative impact to handle resulting water release performance with amphipathic multipolymer.But the example of the hydrophobicity of the copolymerization that this type of is useful dilution comonomer comprises vinylbenzene, vinyl toluene, vinyl-acetic ester, (methyl) vinyl cyanide, n-alkyl (methyl) acrylamide and alkene.
Amphipathic multipolymer can prepare wetting ability and hydrophobic monomer polymerization by any conventional polymerization technique.We have found a kind of this polymeric preferred version that carries out, and promptly use a kind of water-soluble radical initiator to carry out general letex polymerization, and initiator concentration is about 0.1%(weight of total monomer weight) to about 3%(weight).This polymerization preferably uses chain-transfer agent (for example mercaptan) to control molecular weight, at about 40 ℃ to about 100 ℃, carries out under preferred about 50 ℃-70 ℃ temperature.It is about 2500 that the weight-average molecular weight of useful in the methods of the invention amphipathic multipolymer is low to moderate, high to about 100000, preferably is lower than about 50000.This polymerization can be by making the polymerization or carry out fully substantially until polymerization by progressively adding monomer together of all monomers.Remaining unreacted monomer can be introduced in the polymkeric substance by adding initiator in technology well known in the art.The solids concn of the amphipathic nature polyalcohol of polymerization gained in non-organic solvent is low to moderate paramount about 60% solid of about 20% solid.
Treatment process of the present invention is included in pretan or the tanning operation and handles leather with selected amphipathic copolymer dispersion.The multipolymer amount that is used for handling leather accounts for about 0.09% solid (weight) of leather (weight) to about 20% solid (weight), preferred about 0.35% solid (weight) is to about 10% solid (weight), and most preferably from about 1% solid (weight) is to about 5% solid (weight).We repair the performance of estimating this amphipathic multipolymer with the relative difficulty or ease of isolating by relatively use and do not use the extruding of leather behind the selected amphipathic copolymer dispersion in pretan.
The following example is used for illustrating the present invention, and unrestricted the present invention.Other application of the present invention are understood to those skilled in the art.
Embodiment 1: the preparation of amphipathic multipolymer
70%(weight) 2-ethylhexyl acrylate/30%(weight) methacrylic acid
Be aggregated in one 1 liter the four neck round-bottomed flasks and under nitrogen atmosphere, carry out.This flask is equipped with a Teflon on the neck in the central
RPaddle agitator also is equipped with a thermometer and a reflux condensing tube in addition.With the 185g deionized water, 4g sodium lauryl sulphate, 1 sulfuric acid and 0.3g 1%(weight) copperas solution add in the flask.Then with mixture heating up to 60 ℃.Monomer (140g vinylformic acid 2-ethylhexyl ester and 60g methacrylic acid) and the positive Dodecyl Mercaptan chain-transfer agent of 10g are by 95g deionized water and the emulsification of 4g sodium lauryl sulphate, be dissolved in the sodium bisulfite that ammonium persulphate in the 22g water and 0.6g be dissolved in the 22g water together with initiator-0.6g then and added simultaneously in 3 hours in the reaction flask, reaction mixture temperature maintains 60 ℃.Once adding 0.1g redox radical initiator behind reinforced the end makes any residual monomer become polymkeric substance.The cooling polymer emulsion adds 20.4g 13% aqueous sodium hydroxide solution and regulates pH then.The finished product contain 37.8% solid (weight), and the pH value is 5.5.The weight-average molecular weight of polymkeric substance is that benchmark is 8200 through gel permeation chromatography with the acrylic copolymer, and number-average molecular weight is 6600.
Embodiment 2: the preparation of leather
Following flow process is used for preparing and is used for extruding, is the tan leather of repairing and isolating subsequently.The rawhide that two lump limes isolate (lime split) is used for experiment:
Under 90 Fahrenheit degrees, washed 20 minutes
Add: 1% ammonium sulfate-operation 15 minutes
Add: 1% ammonium sulfate
0.06% deliming alkali lye (Bate)
0.2%Triton N-101 tensio-active agent-operation 45 minutes
Under 90 Fahrenheit degrees, washed 15 minutes
Under 65 Fahrenheit degrees, washed 15 minutes
Add: 6% sodium-chlor
1% Leukotan, 1042 acrylic acid seriess synthetic tanning agent-operation 5 minutes
Add: 0.5% formic acid-operation 15 minutes
Add: 0.6% sulfuric acid-2 hours-pH3.8 of operation
Add: 0.2% sulfuric acid-30 minutes-pH3.5 of operation
Add: 3.5%Chromesaver A-31 pretan-2 hours-pH3.2 of operation
Add: 0.5% sodium bicarbonate-operation 15 minutes
Add: 0.5% sodium bicarbonate-operation 30 minutes
Toward rawhide 1
Add: 3% the 70%(weight) 2-EHA/30%(weight) water dispersion of methacrylic acid (37.8% solid)
15 minutes-pH4.2 of-operation
Toward rawhide 2(contrast-outside the scope of the invention)
Add: 3% Leukotan, 1028 acrylic acid seriess synthetic tanning agent-15 minutes-pH5.68 of operation
Spend the night these rawhides are open and flat, push then, repair.Rawhide 1 fine extruding and finishing can be compared with the leather of the full chrome tanning system of standard.Correlated rawhide 2 does not resemble good extruding and finishing the rawhide 1.In general, the characteristics of the rawhide of in the end not handling with acrylic copolymer of the present invention in the step are bad extruding.Therefore, because rawhide is viscosity, they can not be repaired and isolate and be suitable for following process.
Claims (12)
1, a kind of method of improving extruding in the leather processing, repairing and isolate operation, this method comprises: the dispersion with a kind of amphipathic multipolymer in pretan or tannery is handled leather, and this multipolymer is by extremely forming less than at least a hydrophilic monomer of 50% (weight) with greater than 50% (weight) at least a hydrophobic comonomer less than 90% (weight) greater than 10% (weight).
2, the process of claim 1 wherein that above-mentioned multipolymer is by greater than about 15%(weight) to less than about 45%(weight) at least a hydrophilic monomer and greater than about 55%(weight) extremely less than about 85%(weight) at least a hydrophobic comonomer form.
3, the process of claim 1 wherein that above-mentioned multipolymer is by greater than about 20%(weight) to less than about 40%(weight) at least a hydrophilic monomer and greater than about 60%(weight) extremely less than about 80%(weight) at least a hydrophobic comonomer form.
4, the process of claim 1 wherein that above-mentioned amphipathic multipolymer forms by aqueous emulsion polymerization, and this amphipathic multipolymer exists with the form of water dispersion.
5, the process of claim 1 wherein that the weight-average molecular weight of above-mentioned amphipathic multipolymer is about 2500 to about 50000.
6, the process of claim 1 wherein that the above-mentioned hydrophilic polymerized monomer that is used for preparing amphipathic multipolymer is at least a kind of monomer that is selected from water-soluble olefinic unsaturated acid or alkaline monomer or its mixture.
7, the method for claim 6, wherein above-mentioned hydrophilic polymerized monomer is selected from: vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, toxilic acid and this type of sour acid anhydride; (methyl) acrylate that acid replaces, replacement (methyl) acrylate and (methyl) acrylamide of (methyl) acrylamide that acid replaces and alkalescence.
8, the process of claim 1 wherein that the above-mentioned hydrophobic comonomer that is used for preparing amphipathic multipolymer is at least a being selected from (methyl) alkyl acrylate, elementary alkene, the monomer of alkyl carboxylic acid vinyl acetate and their mixture.
9, the method for claim 8, wherein above-mentioned hydrophobic comonomer further is selected from: vinylformic acid C
4-C
12Alkyl ester, methacrylic acid C
4-C
12Alkyl ester, C
4-C
121-alkene, and C
4-C
12The alkyl carboxylic acid vinyl acetate.
10, the method for claim 8, wherein above-mentioned hydrophobic comonomer further comprise be less than 50%(weight) one or more second hydrophobic comonomers, this kind monomer is selected from vinylbenzene, vinyl toluene, vinyl-acetic ester, (methyl) vinyl cyanide and n-alkyl (methyl) acrylamide and alkene.
11, the process of claim 1 wherein that above-mentioned amphipathic multipolymer comprises about 20%(weight) to about 60%(weight) solution or dispersion.
12, the leather that makes by the method for claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US125,876 | 1987-11-27 | ||
| US12587693A | 1993-09-23 | 1993-09-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1109509A true CN1109509A (en) | 1995-10-04 |
| CN1046959C CN1046959C (en) | 1999-12-01 |
Family
ID=22421864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94116442A Expired - Fee Related CN1046959C (en) | 1993-09-23 | 1994-09-23 | Method of improving leather treatment |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0646651A3 (en) |
| CN (1) | CN1046959C (en) |
| AU (1) | AU684529B2 (en) |
| BR (1) | BR9403821A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012073210A1 (en) * | 2010-12-02 | 2012-06-07 | Basf Se | Process for producing leather and aqueous formulations suited therefor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5820633A (en) * | 1996-09-20 | 1998-10-13 | Lesko; Patricia Marie | Method of treating leather with improved retaining agents |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3013912A1 (en) * | 1980-04-11 | 1981-10-29 | Röhm GmbH, 6100 Darmstadt | POLYMER PRODUCTS FOR TREATING BLOSSOMS AND LEATHER |
| US4526581A (en) * | 1983-02-07 | 1985-07-02 | Rohm And Haas Company | Process for producing leather |
| TNSN89128A1 (en) * | 1988-12-02 | 1991-02-04 | Rohn And Haas Company Independance Mall West | LEATHER TREATMENT WITH SELECTED AMPHIPHITE COPOLYMERS |
| US5348807A (en) * | 1991-02-05 | 1994-09-20 | Rohm And Haas Company | Polymeric retan fatliquor for low fogging upholstery leather |
| DE4214011C1 (en) * | 1992-04-29 | 1993-11-04 | Muenzing Chemie Gmbh | COPOLYMERISATE |
-
1994
- 1994-09-19 EP EP94306833A patent/EP0646651A3/en not_active Withdrawn
- 1994-09-20 AU AU73070/94A patent/AU684529B2/en not_active Ceased
- 1994-09-22 BR BR9403821A patent/BR9403821A/en not_active IP Right Cessation
- 1994-09-23 CN CN94116442A patent/CN1046959C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012073210A1 (en) * | 2010-12-02 | 2012-06-07 | Basf Se | Process for producing leather and aqueous formulations suited therefor |
| CN103237903A (en) * | 2010-12-02 | 2013-08-07 | 巴斯夫欧洲公司 | Process for producing leather and aqueous formulations suited therefor |
| CN103237903B (en) * | 2010-12-02 | 2016-04-06 | 巴斯夫欧洲公司 | Produce the method for leather and be applicable to this aqueous formulation |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0646651A3 (en) | 1996-09-18 |
| BR9403821A (en) | 1995-05-23 |
| AU684529B2 (en) | 1997-12-18 |
| AU7307094A (en) | 1995-04-06 |
| CN1046959C (en) | 1999-12-01 |
| EP0646651A2 (en) | 1995-04-05 |
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| PB01 | Publication | ||
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |