CN101111611A - Method for preparing wet-type pink leather - Google Patents
Method for preparing wet-type pink leather Download PDFInfo
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- CN101111611A CN101111611A CNA2004800448563A CN200480044856A CN101111611A CN 101111611 A CN101111611 A CN 101111611A CN A2004800448563 A CNA2004800448563 A CN A2004800448563A CN 200480044856 A CN200480044856 A CN 200480044856A CN 101111611 A CN101111611 A CN 101111611A
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- tanning
- zirconium
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Abstract
A process of combination tannage is disclosed whereby Zirconium salt is complexed with THP salt to produce wet pink leather without using any conventional dye. The resulting leathers exhibit shrinkage temperature of more than 100 DEG C properties and other comparable to those of conventionally processed leathers.
Description
Invention field
The invention provides a kind of method of utilizing inorganic and combination organic chemicals to prepare wet-type pink (wet pink) leather.Imagine this method and in the leather processing industry of preparation pink leather, have huge potential application, need not to use any traditional dyestuff.
Background of invention
Leather processing consists essentially of pre-tanning, tanning and back tanning operation, is finishing subsequently.Pre-tanning comprise sequence of operations as soak into, liming, deliming, softening and pickling, it makes rawhide and fur reach the condition of tanning subsequently basically.
Leather need dye with different tones, and this depends on the requirement by its consumer's goods that make.The dyeing of leather is generally back tanning wet type operation, and it often utilizes different conventional dyestuffs such as acid dye, substantive dyestuff, metal complex dyes to wait and carry out.Impel the investigator to explore to be used to develop the ecological friendly possibility of selecting of colored leather about the appearance of the environmental concern of the toxic component relevant with these dyestuffs.
Verified, the different dyes that is used for tanning is brought particular color on the leather of tanning.The vegetable tanning material that is generally used for the leather tanning produces brown leather.By utilizing metal-salt can make the leather of the vegetable tannages of different tones as eater (striker).For example, vegetable tanning material with molysite combination, makes black leathers, as (Journal of Societyof Leather Technologists and Chemists, 86,106-111,2002) such as Raghava Rao studied like that.
Though report does not utilize the vegetable tannages method to prepare pink leather with any metal attack thing, the main limitation relevant with vegetable tanning material is that they cause over load, and it has reduced the multifunctionality that the leather that obtains is made different final products.In addition, also known plant tannic acid is to be difficult to biodegradable material.
Along with the appearance of mineral tanning agent, chromium has formed topmost tanning agent, and it obtains blue coloured leather, generically is called wet blue.In the method, utilize basic chromium sulphate with pickling pelt (hides/skins) tanning.Though chromium (III) salt is used for leather processing in a large number, the environmental concern that causes owing to pollution of chromium impels research alternate tanning agent.
Among other mineral tanning agent, Selverangam etc. (Leather Science, 11,383,431,1964) have studied the potentiality that aluminium is used for tanning; Coyington (Journal ofAmerican Leather Chemists Association 82,1,1987) has studied the tanning potentiality of titanium; (Journal of Society of Leather Technologistsand Chemists 82 such as Gaidau, 143,1998) (Journal of American Leather Chemists Association such as the tanning potentiality of iron and Sreeram have been reported, 95,324,2000) explored the possibility of zirconium as tanning agent.But all there be the inherent defect relevant with them in each, as (Journal of American Leather ChemistsAssociation, 97,189,2002) such as Madhan emphasized like that.Though aluminium and titanium tannage leather make white leather, they have poor hydrothermal stability.There is the deepening of color in the leather of iron tanned leather between aging time, and also has poor strength characteristic.
The leather of zirconium tanned leather often than make by chrome tanned leather those more complete sum is firmer.Sreeram etc. have obtained the patent (Indian patent application No.3077/DEL/98) of preparation based on the method for the new organometallic polymer matrix of zirconium.The leather that so makes has pleasant white, has good light fastness, and is better than the leather of aluminum tanning leather and has the shrinkage temperature of higher (being higher than 90 ℃).Zirconates tends to have very big convergency, and makes tight, firm leather usually; Cause the quick tanning of particulate and on suede, produce thin, short fine hair.Shelter salt such as acetate by use, can reduce convergency, obtain soft, smooth particulate leather, as Madhan etc. study (Journal of American LeatherChemists Association 98,107-114,2003).The main limitation relevant with zirconium tanned leather be, zirconates precipitates with basic salt being higher than under 2.0 the pH.Another limitation relevant with this tanning is that known zirconium tanned leather makes the leather with drawn grain.But, not general about the disadvantageous effect or the toxic report of zirconates.Thus, utilizing the tanning of zirconates will be ecological friendly selection.
Das Gupta (Journal of Society of Leather Technologists andChemists, 86,188,2002) has carried out the research about the tanning performance of tetrakis hydroxymethyl phosphonium salt (THP), as the tanning agent of the replacement of traditional chrome tanned leather system.Burrow etc. have studied the tanning potentiality (US6,685,747) of THP and chromium.Studied the combination of THPS to the influence of the shrinkage temperature of slunks and they and aluminium salt.The advantage of THPS comprises hypotoxicity, reduction process level, quick disintegration and lifeless matter cylinder accumulation in environment.When replacing bigger toxic sterilant, the THPS sterilant provides human health and the two lower risk of environment.
Can not obtain in the prior art not use any dyestuff or pigment to prepare peach leather in the tanning stage.
Goal of the invention
Main purpose of the present invention provides a kind of method for preparing wet-type pink leather.
Another object of the present invention provides a kind of method of utilizing zirconium and THPS salt to prepare wet-type pink leather.
Still another purpose of the present invention provides a kind of leather tanning that more complete, softer and more slick leather are provided.
Still another purpose of the present invention is, from tetrakis hydroxymethyl phosphonium vitriol (THPS), tetrakis hydroxymethyl phosphonium hydrochloride (THPC) individually or arbitrary combination ground select tetrakis hydroxymethyl phosphonium salt.
Still another purpose of the present invention is, from basic zirconium chloride and zirconium sulfate individually or arbitrary combination ground select zirconates.
Still another purpose of the present invention provides a kind of ecological friendly and leather tanning that reduce pollution of chromium.
Summary of the invention
Thus, the invention provides a kind of method for preparing wet-type pink leather, this method comprises: handle pickling 0.5-3 hour time period of hides/skins under the pH of 2.5-3.0 scope in the presence of the common salt aqueous solution (concentration is 6-6.5Be ') of 20-100%w/v with the tetrakis hydroxymethyl phosphonium salt (THP salt) of 0.5-3%w/w, use the zirconates of 5-10%w/w and the organic ligand of 1-3%w/w (to be selected from tartrate subsequently, citric acid, Whitfield's ointment and phthalic acid and/or their sodium salt) hides/skins of acquisition is not less than 1 hour time in the treatment step (i) under dynamic condition (dynamic condition), by ordinary method pH regulator is arrived 4.8-5.0 subsequently, make wet-type pink leather thus.
Detailed Description Of The Invention
Describe method of the present invention below in detail:
Under the pH of 2.5-3.0 scope, handle pickling 0.5-3 hour time period of hides/skins in the presence of the common salt aqueous solution (concentration is 6-6.5Be ') of 20-100%w/v with the tetrakis hydroxymethyl phosphonium salt (THP salt) of 0.5-3%w/w.The hides/skins that obtains is handled under dynamic condition with the zirconates of 5-10%w/w and the organic ligand of 1-3%w/w (being selected from tartrate, citric acid, Whitfield's ointment and phthalic acid and/or their sodium salt).After being not less than time period of 1 hour, utilize alkali with the pH regulator of dye bath to 4.8-5.0, obtain wet-type pink leather thus.
Creativeness of the present invention is to have obtained pink painted by the mode of the complexing action between zirconium and the THP, its wavelength by the ultraviolet-visible spectrum of zirconium-THP salt tanning solution is observed to moving of visible wavelength region, need not to use any conventional dyes just to make wet-type pink leather thus.
In another embodiment of the present invention, starting material are selected from fur and the rawhide of goat, sheep, pig, cow and buffalo.
In still another embodiment of the present invention, tetrakis hydroxymethyl phosphonium salt individually or arbitrary combination be selected from tetrakis hydroxymethyl phosphonium vitriol (THPS) and tetrakis hydroxymethyl phosphonium hydrochloride (THPC).
Among the present invention, THPC and THPS individually or arbitrary combination ground use.THP is required main active component.Thus, there is not concrete combination, because provide THP all to satisfy purpose of the present invention in any way.
In another embodiment of the present invention, organic ligand is selected from tartrate, citric acid, Whitfield's ointment and phthalic acid and/or their sodium salt.
In another embodiment of the present invention, employed zirconates individually or arbitrary combination be selected from basic zirconium chloride and zirconium sulfate.Metallic Z r is the required main active component of tanning.Thus, there is not concrete combination, because provide Zr all to satisfy purpose of the present invention in any way.
In another embodiment of the present invention, during handling hides/skins with tetrakis hydroxymethyl phosphonium salt (THP), the alkali that is selected from sodium bicarbonate and sodium formiate by use is regulated pH.
In another embodiment of the present invention, obtain wet-type pink leather by the complexing action between zirconium and the THP salt, its wavelength by the ultraviolet-visible spectrum of zirconium-THP salt tanning solution is realized to moving of visible wavelength region.
In another embodiment of the present invention, this method makes soft and level and smooth leather.
The following example only provides and should not be construed as limiting the scope of the invention thus in the mode of explanation.
Embodiment 1
The pickling goatskin that to get three weight be 2.7kg.The pickling fur is charged to has in the rotary drum of 540ml salt solution that concentration is 6Be ' and pH is 2.5.So far, 40.5g THPS is added in this rotary drum.Rotation duration is 30 minutes.202.5g basic zirconium chloride and 67.5g sodium tartrate are added in this rotary drum.This rotary drum was rotated 60 minutes.At last, utilize 13.5g sodium formiate and 81g sodium bicarbonate to be basified to pH4.8.The fur of tanning is used 5400ml water washing 10 minutes, drain water and obtain wet-type pink leather.
Embodiment 2
The pickling lamb skin that to get three weight be 4.0kg.The pickling fur is charged to has in the rotary drum of 4000ml salt solution that concentration is 6.5Be ' and pH is 2.8.So far, 20g THPC is added in this rotary drum.Rotation duration is 60 minutes.200g zirconium sulfate and 40g citric acid are added in this rotary drum.This rotary drum was rotated 90 minutes.At last, utilize 20g sodium formiate and 120g sodium bicarbonate to carry out routine and be basified to pH4.9.The fur of tanning is used 8000ml water washing 10 minutes, drain water and obtain wet-type pink leather.
Embodiment 3
The pickling cow side skin (cow side) that to get four weight be 25kg.Pickling side leather jacket is expected to have in the rotary drum of 18750ml salt solution that concentration is 6.3Be ' and pH is 3.0.So far, 300g THPS and 200gTHPC are added in this rotary drum.Rotation duration is 120 minutes.2500g basic zirconium chloride and 650g sodium phthalate and 100g Whitfield's ointment are added in this rotary drum.This rotary drum was rotated 180 minutes.At last, utilize 125g sodium formiate and 750g sodium bicarbonate to carry out routine and be basified to pH5.0.The fur of tanning is used 50000ml water washing 10 minutes, drain water and obtain wet-type pink leather.
Embodiment 4
The light yellow calf skin of pickling that to get three weight be 18kg.The pickling fur is charged to has in the rotary drum of 18000ml salt solution that concentration is 6.5Be ' and pH is 2.8.So far, 540g THPS is added in this rotary drum.Rotation duration is 180 minutes.900g basic zirconium chloride, 900g zirconium sulfate, 180g phthalic acid and 180g Trisodium Citrate are added in this rotary drum.This rotary drum was rotated 180 minutes.At last, utilize 90g sodium formiate and 540g sodium bicarbonate to carry out routine and be basified to pH5.0.The fur of tanning is used 36000ml water washing 10 minutes, drain water and obtain wet-type pink leather.
Advantage
Be advantage of the present invention below:
1. do not use dyestuff and pigment to make pink leather.
2. the method is almost without any need for the control measure of complexity.
3. it has thoroughly got rid of alkaline sulfuric acid chromium.
4. be applicable to the raw material of all types.
5. this tanning system makes complete, soft and smooth leather.
6. the method has been utilized commercially available chemicals.
Claims (11)
1. the method for preparing wet-type pink leather, described method comprises step:
I) provide the pickling hides/skins, its tetrakis hydroxymethyl phosphonium salt (THP salt) of having used 0.5-3%w/w in the presence of the common salt aqueous solution of 20-100%w/v, under predetermined pH, handled the preset time section and
The hides/skins of ii) using the organic ligand of the zirconates of 5-10%w/w and 1-3%w/w to obtain in the treatment step (i) under dynamic condition is not less than 1 hour time, subsequently by ordinary method with pH regulator under preset value, make wet-type pink leather thus.
2. the described method of claim 1, wherein these starting material are selected from fur and the rawhide of goat, pig, sheep, cow and buffalo.
3. the described method of claim 1, wherein the concentration range of salt is 6-6.5Be ' in the aqueous solution.
4. the described method of claim 1, wherein in the step (i), described predetermined pH scope is 2.5-3.0, and described preset time segment limit is 0.5-3 hour.
5. the described method of claim 1, wherein tetrakis hydroxymethyl phosphonium salt individually or arbitrary combination be selected from tetrakis hydroxymethyl phosphonium vitriol (THPS) and tetrakis hydroxymethyl phosphonium hydrochloride (THPC).
6. the described method of claim 1, wherein this organic ligand is selected from tartrate, citric acid, Whitfield's ointment and phthalic acid and/or their sodium salt.
7. the described method of claim 1, wherein step (ii) in, predetermined range is 4.8-5.0.
8. the described method of claim 1, wherein step (ii) in, the ordinary method of regulating pH is the alkali that is selected from sodium bicarbonate and sodium formiate by use.
9. the described method of claim 1, wherein employed zirconates individually or arbitrary combination be selected from basic zirconium chloride and zirconium sulfate.
10. the described method of claim 1 wherein obtains wet-type pink leather by the complexing action between zirconium and the THP salt, and its wavelength by the ultraviolet-visible spectrum of zirconium-THP salt tanning solution is realized to moving of visible wavelength region.
11. the described method of claim 1, wherein this method makes soft and level and smooth leather.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004800448563A CN101111611A (en) | 2004-12-22 | 2004-12-22 | Method for preparing wet-type pink leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004800448563A CN101111611A (en) | 2004-12-22 | 2004-12-22 | Method for preparing wet-type pink leather |
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| Publication Number | Publication Date |
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| CN101111611A true CN101111611A (en) | 2008-01-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2004800448563A Pending CN101111611A (en) | 2004-12-22 | 2004-12-22 | Method for preparing wet-type pink leather |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851828A (en) * | 2010-01-16 | 2010-10-06 | 张立文 | Reducing leather and preparation method thereof |
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2004
- 2004-12-22 CN CNA2004800448563A patent/CN101111611A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851828A (en) * | 2010-01-16 | 2010-10-06 | 张立文 | Reducing leather and preparation method thereof |
| CN101851828B (en) * | 2010-01-16 | 2012-09-05 | 张立文 | Reducing leather and preparation method thereof |
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