CN1474876A - Tannages and tanning material - Google Patents
Tannages and tanning material Download PDFInfo
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- CN1474876A CN1474876A CNA018187838A CN01818783A CN1474876A CN 1474876 A CN1474876 A CN 1474876A CN A018187838 A CNA018187838 A CN A018187838A CN 01818783 A CN01818783 A CN 01818783A CN 1474876 A CN1474876 A CN 1474876A
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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
- C14C3/10—Vegetable tanning
- C14C3/12—Vegetable tanning using purified or modified vegetable tanning agents
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Abstract
A novel tannage comprises the reaction product of a quaternary phosphonium compound (e.g. tetrakis hydroxymcthyl phosphonium chloride or sulphate) with a vegetable tanning agent (e.g. mimosa, chestnut, wattle, tara, myrobolam or quebracho). There is also provided a method for the production of such a tannage.
Description
Invention field
The present invention relates to a kind of new tanning compound of tanning rawhide finished leather.Use the skin of tanning of this compound to handle and under without the situation of chromium, to carry out.
The invention still further relates to the method for preparing tanning material, these tanning materials comprise the reaction product of quaternary phosphonium compound with natural tanning agent.In addition, the present invention relates to by the prepared tanning material of this method, these tanning materials in handling animal hides application and the skin of tanning that obtains whereby.
Background of invention
The processing of rawhide is always needed to use tanning compound based on chromium, used main tanning agent in the current world wide.Chromium but is to think the disagreeableness toxic metal compound of environment at present.But when make great efforts satisfying the more strict regulation that link mutually with chromium and solid waste disposal and product safety and repeating utilization factor and require, for the pressure normal incidence increase of producing the Chrome-free leather along with leather industry.Some European countries have now begun to limit the use that contains the chromium leather.Some other tanning agent are on probation already, and as the double salt of aluminum chloride, Tai-Ace S 150, titanium sulfate and Tai-Ace S 150 and titanium, but these tanning agent all do not produce the leather that has as with the resultant hydro-thermal characteristic of chromium.Also studied other organometallic aluminium chromium complex, and established patent [English Patent 2153844 (1984)] about the application of the alkali formula al formate that contains poly carboxylic acid or aluminum acetate.This tanning agent, measured just as shrinkage temperature by its leather, provide the hydrothermal stability that is analogous to chromium, but and the problem of more unresolved environment connections.Synthetic tanning agent used about 90 years.These tanning agents mostly are the condensation product based on naphthalene or phenol-formaldehyde greatly.The leather that they produce has roughly 70-75 ℃ shrinkage temperature.These leathers can not be compared with containing the chromium leather on its characteristic.Oxazolidine [English Patent 1481508 (1973)], tetrakis hydroxymethyl phosphonium chloride [United States Patent (USP) 2732278 (1956)] and four methylol phosphonium salts [new zealand patent 244515 (1977)] are environmental friendliness, but the leather that provides has only about 85 ℃ shrinkage temperature.And they do not produce gratifying leather when using separately.Have only then with chromium or vegetable tannages agent in addition these reagent of tanning just provide gratifying leather.
At US 2,732, disclosed a kind of two step tanning methods in 278, it requires with the tetrakis hydroxymethyl phosphonium chloride tanning agent, follows again with the vegetable tanning material tanning agent.The shrinkage temperature of these leathers is no more than 90 ℃.
Therefore, simple no chrome tanned leather method and the demand that can be used for the tanning material compound of this tanning method are still existed.
Summary of the invention
First aspect the invention provides a kind of tanning material, and its molecular formula is:
A is the tanning agent that contains polyphenol in the formula, and R
1, R
2And R
3Then be selected from OH or X, wherein X is muriate, vitriol or phosphoric acid salt, and condition is at R
1, R
2And R
3In have only one to be X.
Second aspect the invention provides a kind of method for preparing tanning material.This tanning material comprises the reaction product of a Yi quaternary phosphonium compound and a vegetable tannages agent, according to this method can have water or anhydrous in the presence of will be by weight ratio be that 1: 5 or bigger this phosphonium compounds and vegetable tannages agent mix, make this mixture reach 20 hours subsequently in minimum 80 ℃ temperature heating.
The present invention further provides the tanning material that is prepared by the described method of last joint.
The present invention also further provides and uses this tanning material in the processing of animal hides, and the tanning skin through handling like this.
Tanning agent A is preferably a kind of vegetable tannages agent.
The present invention further provides a kind of method of tanning rawhide, and this method comprises the tanning compound treatment rawhide of the present invention with 1 to 30% weight (based on the weight of rawhide).
Most desirably, this tanning is handled and is being carried out between 2.5 to 8.5 pH with 10 ℃ to 45 ℃ temperature.
As a preliminary step or further step, this method comprises with another tanning agent handles rawhide.
Although the present invention generally as mentioned above, those of skill in the art can understand, and the invention is not restricted to this, but the embodiment that the embodiment that provides is described below also is provided.
Detailed Description Of The Invention
First aspect present invention provides a kind of tanning material, and its molecular formula is:
A is the tanning agent that contains polyphenol in the formula, and R
1, R
2And R
3Then be selected from OH or X, wherein X is muriate, vitriol or phosphoric acid salt, and condition is at R
1, R
2And R
3In have only one to be X.
X is preferably muriate or vitriol.
Tanning agent A is preferably a kind of vegetable tannages agent.Any suitable vegetable tannages agent as known in the art all can be used.Preferred vegetable tannages agent comprises its condensation or hydrolytic reagent, for example mimosa extract, grain wood tannin extract, wattle extract, Caesalpinia spinosaKuntze collection, the sub-tannin extract in river and quebracho extract, but be not limited to these.
Will appreciate that as the reader, novel tanning material of the present invention is a kind of condenses, can be synthesized with tetrakis hydroxymethyl phosphonium chloride and tetra methylol vitriol by condensation vegetable tannages agent discussed above, condensation is to carry out according to known method of condensing or as the method that is proposed here.
In manufacturing a kind of preferred method of such tanning material, this tanning material synthesizes with 75 to 35 parts, a kind of Si methylol phosphonium reactant salt of being preferably 35 to 45 parts by a kind of condensed vegetable tanning agent that makes 25 to 65 parts, is preferably 45 to 50 parts.This method can comprise the water that uses 0-15% in addition, and 30 ℃ to 60 ℃, be preferably 40 ℃ to 50 ℃ temperature and constantly stir under carry out 2 to 6 hours, be preferably 4 hours.
Under above-mentioned operational condition, perhaps Gai quaternary phosphonium compound can not all react with this tanning agent, therefore should be removed as unwanted byproduct of reaction.
We find now, by reducing with respect to the consumption of tanning agent De quaternary phosphonium compound and the temperature and time that increases reaction, we just can make the tanning material that Can Liu phosphonium compounds total amount wherein is reduced to minimum or is eliminated, and this tanning material presents commercial useful tanning characteristic when being applied to animal hides.
The most beyond thoughtly be, we also find can be by the reaction of vegetable tannages Ji Tong phosphonium compounds, and producing same useful Gai phosphonium compounds of tanning material ， is the four (condensation products of methylol) phosphonium salt and urea, thiocarbamide or amine.
Therefore in second aspect, the invention provides a kind of method of producing tanning material, this tanning material comprises the reaction product of quaternary phosphonium compound with the vegetable tannages agent, Gai phosphonium compounds and vegetable tannages agent are mixed in the presence of randomly at water by 1: 5 or bigger weight ratio according to this method, then make this mixture reach 20 hours minimum 80 ℃ temperature heating.
The present invention further provides a kind of tanning material of producing by the method described in the last joint.
The present invention further provides again and uses this tanning material in the processing of animal hides and the tanning skin of in addition handling like this.
The Ci quaternary phosphonium compound is preferably Yi Zhong phosphonium salt, such as four (methylol) Liu Suan Phosphonium (after this being abbreviated as THPS) or four (methylol) phosphonium chlorides (after this being abbreviated as THPC).
On the other hand, the Ci quaternary phosphonium compound can comprise the condensation product of the organic nitrogen compound of THPS or THPC and picture urea, thiocarbamide or amine and so on.
This vegetable tannages agent is preferably the tanning agent of a kind of condensation or hydrolysis, for example Touch-me-notAction Plant, wattle, chestnut, quebracho, Caesalpinia spinosaKuntze or myrobalan.Most preferably this vegetable tannages agent be for a kind of condensation such as the Touch-me-notAction Plant tanning agent.
The present invention further provides a kind of method of tanning rawhide, and the tanning material compound of the present invention (all the percentage number averages are based on the weight of rawhide) that this method comprises with 1 to 30%, be preferably 5 to 25%, be most preferably 10-15% weight is handled rawhide.
It is desirable to, this tanning handle be 2.5 to 8.5 at pH, be preferably 4.0 to 6.5, be most preferably between 4.4 to 6.5, and temperature is 15 ℃ to 45 ℃, is preferably 20 ℃ to 40 ℃ and be most preferably 35 ℃ and carry out.
This tanning is handled can reach 2 to 10 hours, more preferably is 4 to 8 hours, and is most preferably 4 hours.
According to the method according to second aspect present invention, its reaction can be suitable for carrying out in the presence of water.For example, this reaction mixture can comprise the quaternary phosphonium compound of 12.5% weight, the vegetable tannages agent of 50% weight and the water of 37.5% weight, and all the percentage number average calculates according to the gross weight of this reaction mixture and the gross weight of every kind of reagent.In this description, " gross weight " comprises " activity " and " nonactive " weight of reagent out of the ordinary.
We find, reach about 20 hours at 80 ℃ of these reaction mixtures of heating, cause Gai quaternary phosphonium compound and vegetable tannages agent complete reaction basically, as by such as nmr analysis proved.Found that short reaction times causes the inevitable residual of little reaction completely and this reaction mixture Zhong Zhi phosphonium compounds.
In another preferred embodiment, tanning is handled and is also used a kind of aluminium tanning agent, such as the aluminium salt that is selected from aluminum chloride, Tai-Ace S 150, aluminum acetate and al formate, but is not limited to those equally.The aluminium salt concn of being used in can managing herein is 0.1 to 5% by the weight of rawhide, is preferably 0.5 to 2%.
The applicant finds, uses aluminium salt with novel tanning material compound of the present invention, will increase the shrinkage temperature of resultant leather to the scope from 98 ℃ to 120 ℃.
By a specific preferred method, carried out 30 minutes to 4 hours with novel tanning material compound of the present invention tanning, be preferably 1 hour, thereafter aluminium salt is added.In this preferred method, this aluminium salt is alkali formula al formate, and tanning is then carried out at pH4.0, is generally 6 hours.
This method can further comprise other standard tanning step as known in the art.This makes the skin drying after being included in and making skin degreasing, emulsion oil-filling and the tanning of soaking before the tanning.
Before being preferably in tanning rawhide is soaked, and also can select it is carried out degreasing.
This tanning is handled can comprise pre-tanning step or another a tanning step with known tanning agent tanning.The tanning agent that is used for these additional steps can comprise chromium, aluminium or vegetable tannages agent, but is not limited to these.
Use this novel cpd of the present invention that tanning is realized as a step chromium-free treatment.This just simplifies known technical process, significantly reduces the influence to environment, still forms the high skin of hydrothermal stability simultaneously.In addition, test shows, and handle by two steps of adopting four methylol phosphonium salts and similar succeeded by the leather of independent tanning step tanning, the performance of leather characteristic that produces can compare with containing chromium performance of leather characteristic.Significantly increase representedly as the hydrothermal stability of the rawhide of tanning, this novel tanning compound is by working with the rawhide proteins react.
The present invention will be illustrated by following unrestriced embodiment.
In embodiment 1 to 9, a kind of compound that on behalf of You phosphonium compounds and chestnut extract reaction, a kind of compound that on behalf of You phosphonium compounds and mimosa extract reaction, " NPM " produced, " NPC " produced.
Embodiment 1
As the compound of independent tanning agent, the application of NPM and compound N PC.
Make in the sheepskin degreasing of pH1.5 immersion and with pH regulator to 3.5, arbitrarily distribute for using listed various tanning agent tannings in the following table 1.In the dosage drum that computer-controlled per minute 12 changes, to the tanning 5 hours one by one of these rawhides, the pH that tanning is bathed with sodium formiate and sodium bicarbonate brings up to pH5.5 to 6.5 and holding temperature gradually at 35 ℃ according to a standard method.According to the international leather technician chemist described method IUP 16 of association, measure as the metric shrinkage temperature of tanning.Make this leather emulsion oil-filling and skinning according to standard program.Its result is given in following table 1:
Table 1
Shrinkage temperature, ℃
(after the tanning in 5 hours) is single single with mimosa extract 76 compound alone NPM 88 compound alone NPC 89 with Si methylol phosphonium (THPS) 82
This result shows that the tanning of compound N PM and compound N PC is renderd a service and is better than Si methylol phosphonium (THPS) and vegetable tanning material.Generally can make the leather of tanning dry under common tanyard's condition.It is typically hard to be the formaldehyde tan leather after the rawhide drying of THPS tanning, and provides almost white with the rawhide of compound N PM tanning, but the leather of soft and flexure, at feel and similar in appearance East India (E.I) tan leather that can commercial sale.
Embodiment 2
Compound N PM and compound N PC are as the application of pre-tanning agent
Make the sheepskin degreasing of immersion and with its pH regulator to 3.5.According to a standard method, in the dosage drum that a computer-controlled per minute 12 changes, came these rawhides of tanning 5 hours with THPS, with sodium formiate and sodium bicarbonate the pH of tanning bath is brought up to 5.0 to 5.5 and keep its temperature at 35 ℃ gradually.According to the international leather technician chemist described method IUP 16 of association, measure it as the metric shrinkage temperature of tanning.Arbitrarily distribute these skins for doing further tanning then with various known mineral tanning agent.Carry out tanning with novel cpd NPM, known THPS in conjunction with NPM or THPS and different aluminum salt.Its result awards following table 2:
Table 2
Shrinkage temperature, ℃
Single with THPS 82
THPS+ aluminium chlorohydroxide (1%Al
2O
3) 88
THPS+ basic aluminium sulphate (1%Al
2O
3) 87
THPS+ alkali formula al formate (1%Al
2O
3) 88
THPS+ plumbous subacetate (1%Al
2O
3) 89
THPS+ Strontium Sulphate (1%Al
2O
3) 88
THPS+ synthetic tanning material TAL (1%Al
2O
3) 88
Compound alone NPM 90
Compound N PM+ aluminium chlorohydroxide (1%Al
2O
3) 97
Compound N PM+ basic aluminium sulphate (1%Al
2O
3) 98
Compound N PM+ plumbous subacetate (1%Al
2O
3) 99
Compound N PM+ alkali formula al formate (1%Al
2O
3) 100
Single shrinkage temperature that provides leather with THPS is lower than novel tanning compound N PM.The compound tanning material of THPS and aluminium provide than single with novel cpd reached will be low shrinkage temperature.By comparison, novel cpd and known aluminium salt binding, provide higher significantly shrinkage temperature, during especially in conjunction with known alkali formula al formate, coctostabile leather (shrinkage temperature is higher than 100 ℃) when being given in according to the method test described in the IUP 16 of international leather technician chemist association.
Embodiment 3
The cooperation tanning of the concentration effect of compound N PM and alkali formula al formate
Make the sheepskin degreasing of immersion and regulate pH to 3.5.In the dosage drum that a computer-controlled per minute 12 changes,, with sodium formiate and sodium bicarbonate the pH of tanning bath is brought up to pH5.25 gradually, and keep its temperature at 35 ℃ with the compound N PM tanning rawhide of different concns 5 hours.Measure shrinkage temperature according to the international leather technician chemist described method IUP 16 of association.Then with 9.12% alkali formula al formate (1%Al
2O
3) these skins are done further tanning, and tanning is bathed final pH regulator to pH4.4-4.6.As above-mentioned, measure the shrinkage temperature of these skins once more.Make leather emulsion oil-filling and skinning according to standard program.Its result awards following table 3:
Table 3
Shrinkage temperature, ℃
Final tanning after the NPM tanning (after plumbous the processing)
Compound alone NPM
5% compound N PM 87 98
6% compound N PM 88 99
7% compound N PM 87 99
8% compound N PM 87 99
10% compound N PM 88 105
15% compound N PM 90 102
20% compound N PM 90 105
When the skinning leather being done the evaluation of feel and total quality, find to provide optimal results with 10-15% compound N PM.Use the low concentration leather just to seem empty and hard, and use the higher concentration leather just heavy, more plentiful and darker.
Embodiment 4
Compound N PM and alkali formula al formate cooperate the application of tanning
Make the sheepskin degreasing of immersion and regulate pH to 3.5.With 15% compound N PM these skins of tanning 5 hours in computer-controlled dosage drum, gradually the pH of tanning bath is increased to pH5.20 with sodium formiate and sodium bicarbonate simultaneously, and maintains the temperature at 35 ℃.Method IUP 16 according to international leather technician chemist association measures its shrinkage temperatures.(0.5% to 2.0%Al for the alkali formula al formate with different amounts separately and arbitrarily to distribute these skins then
2O
3) do further tanning.Be adjusted to pH3.2 with one group and handle another group and do not reduce its pH with oxalic acid, to conclude tanning effect at different pH combined alkali formula al formates.According to standard program leather is carried out emulsion oil-filling and skinning.Its result awards following table 4:
Table 4
Shrinkage temperature, ℃
The high initial pH of low initial pH
(pH transfers to 3.2) (pH5.28)
Compound alone NPM 90
In conjunction with 0.5%Al
2CO
3Alkali formula al formate 105 110
In conjunction with 0.75%Al
2O
3Alkali formula al formate 106 116
In conjunction with 1%Al
2O
3Alkali formula al formate 111 116
In conjunction with 1.5%Al
2O
3Alkali formula al formate 115 115
In conjunction with 2.0%Al
2O
3Alkali formula al formate 101 105
These results show, 0.5%Al
2O
3Just be enough to provide and be higher than 100 ℃ shrinkage temperature.Also improve shrinkage temperature indistinctively in the percentage concentration that the initial pH of height is higher, and, also need not before adding alkali formula al formate, to reduce pH for to reach the highest shrinkage temperature.Along with the increase of used al formate percentage concentration, the color of leather just become light more, 1%Al
2O
3Provide the leather of best in quality.
Embodiment 5
The cooperation tanning of compound N PM and alkali formula al formate
Make the sheepskin degreasing of immersion and regulate pH to 4.5.Then these skins are divided into three random set.According to standard method, in computer-controlled dosage drum with 10% compound N PM to first group of (group A) tanning 4 hours, the while is brought up to 5.0-5.5 to pH gradually with sodium formiate and sodium bicarbonate, maintains the temperature at 35 ℃.Method IUP16 according to international leather technician chemist association measures its shrinkage temperature.Then in same bath with 9.12% alkali formula al formate (1%Al
2O
3) do further tanning, regulate its pH to 4.4-4.5 gradually.Measure it again and shrink concentration.With second group of 10% compound N PM tanning (group B) 1 hour, then make pH be increased to 4.0.At this moment with 9.12% alkali formula al formate (1%Al
2O
3) add in the identical bath, regulate pH to 4.4-4.5 gradually, keep total tanning time identical with first group.With the 3rd group of 10% a compound N PM tanning (group C) 20 minutes, then in this identical bath, add 9.12% alkali formula al formate (1%Al
2O
3), regulate its pH to 4.4-4.5 gradually, keep total tanning time identical with first group.Measure its shrinkage temperature again.Use 2% Switzerland Sandoderm Brown R then, Clariant makes all organize painted 30 minutes, and carries out emulsion oil-filling and skinning according to a standard program.Its result awards following table 5:
Table 5
Shrinkage temperature, ℃
Neck bottom, neck bottom, group A group B group C tanning time neck bottom spent the night 99 111 102 109 103 104 in 6 hours 99 105 98 107 98 100
These results show, 1%Al
2O
3During about 6 hours total tanning, be enough to provide and be higher than 100 ℃ shrinkage temperature.Long tanning time does not improve its shrinkage temperature.Adding alkali formula al formate with novel tanning agent after 1 hour in pH 4.0 tannings, provide the leather of best in quality, is current preferred system therefore.
Embodiment 6
Tanning with improved compound N PM2
By in the five neck reaction vessels of a laboratory, make 400 gram tetra methylol sulfuric acid phosphoniums (available from the Albrite ﹠amp of Britain; Wilson company) and the mixtures of 150 gram water 45 ℃ thermotonuses, synthesize this tanning compound with the 450 gram mimosa extract powder (available from the wattle exploitation office in South Africa) that add gradually.This is reflected under the continuous stirring carried out 4 hours, and maintain the temperature at 45 ℃ to 50 ℃.The productive rate of reaction is about 86-93% (w/w).After this these compounds of indication will be represented with compound N PM2 in this preparation.Its pH (10% this compound solution) is 2.85 to 3.45.
Make 8 sheepskin degreasings of soaking at pH1.8 and regulate its pH to 4.5.Arbitrarily these skins are divided into 4 groups then.According to a standard method, with first group of the tanning 4 hours in the dosage drum that computer-controlled per minute 12 changes of 15% commercial mimosa extract powder, and holding temperature is at 35 ℃.Method IUP 16 according to international leather technician chemist association measures its shrinkage temperatures.With second group of the tanning 4 hours and keep its temperature in computer-controlled dosage drum of 15% commercial mimosa extract powder at 35 ℃.Measure its shrinkage temperature.In this identical bath, continue further tanning 60 minutes at pH3.9, then with 9.12% alkali formula al formate (1%Al with 20% tetra methylol sulfuric acid phosphonium (75% activity)
2O
3) add in this same bath and operate 1 hour, at this moment regulate its pH to 4.4-4.5 gradually.Measure its shrinkage temperature again.With 10% compound N PM2 the 3rd group of tanning 4 hours in computer-controlled dosage drum, and keep its temperature at 35 ℃.Measure its shrinkage temperature according to described method.In this identical bath with 9.12% alkali formula al formate (1%Al
2O
3) continue further tanning and operate 1 hour, regulate its pH to 4.4-4.5 then gradually.Measure its shrinkage temperature again.The 4th group is chrome tanning system, according to standard method with 6% basic chromium sulfate (33% alkali, 25%CrO
3) carry out.Measurement to its shrinkage temperature is the same.Its result awards following table 6 to 20:
Table 6
Shrinkage temperature, ℃ tanning system was spent the night in 4 hours 6 hours
15% mimosa extract, 76 76 76 76 76 7615% Touch-me-notAction Plant+2%THPS+1%Al at the bottom of the neck at the bottom of the neck at the bottom of the neck
2O
375 76 91 93 118 11910% compound N PM2+1%Al
2O
3-90 97 106 111 116 chromium reagent 89---116 118
According to standard method all these leathers are carried out emulsion oil-filling and skinning then, and its physical property is adjusted and tested according to the methods involving of international leather technician chemist association.Its result awards table 7 to 10.
Table 7: with chromium or not with the comparison of the texture strength of the sheepskin leather of chromium institute tanning
The process for tanning texture breaking weight texture fracture of adopting prolongs
(kilogram) (millimeter) 15% mimosa extract 30.4 9.015% Touch-me-notAction Plants+2%THPS+1%Al
2O
339.4 9.110% compound N PM2+1%Al
2O
335.9 10.7 chromium reagent 36.4 9.9
These data are all represented gratifying intensity and consistent with commercial chrome tanning system leather.
Table 8: with chromium or not with the comparison of the tear strength of the sheepskin leather of chromium institute tanning
The process for tanning tear strength (N/mm) that adopts
Average
15% mimosa extract 51.9 5.3
15% Touch-me-notAction Plant+2%THPS+1%Al
2O
333.4 2.6
10% compound N PM2+1%Al
2O
345.9 4.7
Chromium reagent 45.3 1.6
These data are all represented gratifying tear strength and consistent with commercial chrome tanning system leather.
Table 9: with chromium or not with the tensile strength of the sheepskin leather of chromium institute tanning and the comparison of tension set
Process for tanning tensile strength (the N/mm that adopts
2) tension set (%)
Average average 15% mimosa extract 16.7 5.2 32.5 1.415% Touch-me-notAction Plants+2%THPS+1% 20.0 2.4 37.5 5.8Al
2O
310% compound N PM2+1%, 20.7 1.4 20.2 0.8Al
2O
3Chromium reagent 18.8 1.2 23.1 0.5
These data are all represented gratifying intensity, and consistent with commercial chrome tanning system leather.
Table 10: with chromium or not with the comparison of the pliability observed value of the sheepskin leather of chromium institute tanning
The process for tanning leather softness (BLC value) that adopts
Average 15% mimosa extract 5.6 0.415% Touch-me-notAction Plants+2%THPS+1%Al
2O
34.1 0.610% compound N PM2+1%Al
2O
34.3 0.5 chromium reagent 4.1 0.6
These data are all represented the identical or better of pliability characteristic and commercial chrome tanning system leather.
Embodiment 7
Associating tanning with compound N PM2
Synthesizing of this tanning compound is in the five neck reaction vessels of a laboratory, by making 400 gram tetra methylol sulfuric acid phosphoniums (available from Albrite ﹠amp; Wilson, UK) mixtures with 150 gram water carry out 45 ℃ thermotonuses with the 450 gram mimosa extract powder (available from South Africa Jing Mu exploitation office) that add gradually.This is reflected under the continuous stirring and continued 4 hours, and maintains the temperature at 45 ℃-50 ℃.Its productive rate is about 86-93% (w/w).These compounds of indication will be represented with compound N PM2 thereafter in this preparation.Its pH (10% this compound solution) is 2.85 to 3.45.
This tanning compound synthetic, be by make 45 to 50 parts of commercial mimosa extract powder with 40 parts of tetra methylol sulfuric acid phosphoniums and 10 parts of water 40-45 ℃ and constantly stir under reaction carried out in 4 hours.Thereafter this compound of indication will be represented with compound N PM2 in this preparation.
Make the sheepskin degreasing of soaking and regulate its pH to 4.5 at pH1.6.Then skin arbitrarily is divided into four groups.First group (group A) maintains the temperature at 35 ℃ simultaneously with the tanning 4 hours in a computer-controlled dosage drum of 15% commercial mimosa extract powder.Method IUP 16 according to international leather technician chemist association, measure its shrinkage temperature, in this identical bath, continue further tanning 30 minutes at pH3.90, then add 9.12% alkali formula al formate (1%Al with 2% tetra methylol sulfuric acid phosphonium (75% activity)
2O
3) and operate 1 hour, at this moment regulate its pH to 4.4-4.5 gradually.Measure its shrinkage temperature again.Second group (group B) keeps its temperature at 35 ℃ with the tanning 4 hours in a computer-controlled dosage drum of 15% another commercial mimosa extract powder simultaneously.Measure its shrinkage temperature.In this identical bath, continue further tanning 30 minutes at pH3.90, then add 9.12% alkali formula al formate (1%Al with 2% tetra methylol sulfuric acid phosphonium (75% activity)
2O
3) and operate 1 hour, at this moment regulate its pH to 4.4-4.5 gradually.Measure its shrinkage temperature again.The 3rd group (group C) keeps its temperature at 35 ℃ with 10% compound N PM2 tanning 4 hours in a computer-controlled dosage drum simultaneously.Measure its shrinkage temperature again.Then with 9.12% alkali formula al formate (1%Al
2O
3) add in this identical bath and operate 1 hour, at this moment regulate its pH to 4.4-4.5 gradually.Measure its shrinkage temperature again.The tanning of the 4th group (group D) is identical with the 3rd group, has only before adding al formate to make the pH of this bath reduce to 3.5-4.0 with oxalic acid.
According to a standard method to all these leather emulsion oil-filling and skinning.Its shrinkage temperature result awards following table 11:
Table 11
Shrinkage temperature, ℃
Group A group B group C group D
At the bottom of the tanning time neck at the bottom of the neck at the bottom of the neck at the bottom of the neck
7 hours 114 116 112 119 112 116 114 116
Spend the night 114 115 112 118 112 117 114 117
These results show, in total tanning time of about 6 to 7 hours, and 1%Al
2O
3Be enough to provide and be higher than 100 ℃ shrinkage temperature.Long tanning time does not improve its shrinkage temperature.These leathers are delivered to the precision work under common working condition of commercial tanyard.No problem in these Chrome-free leathers of precision work.This leather is accredited as high-quality and does not have what difference with the gloves dress material sheep leather of commercial chrome tanning system.Painted very evenly and total quality be evaluated as satisfactory.The physical testing that it is carried out according to international leather technician chemist association methods involving the results are shown in table 12 to 15.
Table 12: the texture strength process for tanning texture breaking weight texture fracture without the sheepskin leather of chromium institute tanning prolongs
(kg) (mm) group 27.9 9.7 groups of C of 19.9 9.4 groups of B of A 27.4 9.3 groups of D 21.9 8.6
These data are all expressed gratifying intensity, and consistent with commercial chrome tanning system leather.
Table 13: without tear strength process for tanning breaking weight (N) tear strength (N/mm) of the sheepskin leather of chromium institute tanning
41.3 6.2 34.9 2.9 groups of D 46.5 12.5 52.1 7.1 of 44.8 6.5 32.9 3.3 groups of C of 33.8 3.4 34.0 1.1 groups of B of average average group A
These data are all expressed gratifying tear strength, and consistent with commercial chrome tanning system leather.
Table 14: without tensile strength process for tanning breaking weight (N) tensile strength (N/mm of the sheepskin leather of chromium institute tanning
2)
194.4 27.9 17.9 3.9 groups of D 209.6 51.2 24.0 2.9 of 152.3 42.5 11.7 2.8 groups of C of 140.3 19.2 13.8 1.7 groups of B of average average group A
These data are all expressed gratifying intensity, and consistent with commercial chrome tanning system leather.
Table 15: without the tension set of the sheepskin leather of chromium institute tanning
Process for tanning tension set (%)
Average
Group A 32.5 1.46
Group B 37.5 5.88
Group C 20.2 0.89
Group D 23.1 0.59
These data are all expressed gratifying elongation characteristic, and consistent with commercial chrome tanning system leather.
When being performed an analysis, aluminium content finds that exhausted concentrates tanning and bathes the aluminium (Al) that only contains 77.2ppm.This mother liquor will only contain the aluminium of the 3.8ppm that has an appointment as by the condition dilution of common tanyard and enter waste water stream, it be significantly less than the general toxic concentration standard that is applicable to aquatic organism (if pH is 100ppm greater than 6.5, if pH less than 6.5 be 5ppm).Similarly, according to the method described in the JIS 1041 (Japanese Industrial Standards), when doing free formaldehyde content and analyze, the skinning leather of discovery group B and group C only contains 10.6 and the 19.7mg/kg leather respectively.
Embodiment 8
Synthesizing of this tanning compound is to be undertaken by 45 parts of commercial mimosa extract powder FS are reacted under 45-50 ℃ of also continuous the stirring with 40 parts of tetra methylol sulfuric acid phosphoniums and 15 parts of water.Thereafter this compound of indication will be represented with tanning compd E cofan CSP in this preparation.
Make 18 to soak sheepskin (pH=1.6) degreasing, and regulate pH to 4.5.Arbitrarily dividing these skins then is three groups, and every group contains 6 skins.First group (group A) with 15% commercial mimosa extract powder ME tanning 4 hours in a computer-controlled dosage drum, and keeps its temperature at 35 ℃.Measure its shrinkage temperature according to the international leather technician chemist described method IUP 16 of association.Second group (group B) with 3% tetra methylol sulfuric acid phosphonium (75% activity) tanning 30 minutes, and goes through and gradually pH was increased to pH6.5 with sodium formiate and sodium bicarbonate in 4 hours.Measure its shrinkage temperature according to the international leather technician chemist described method IUP 16 of association.Then, according to existing process for tanning again to the pre-tanning leather of tetra methylol sulfuric acid phosphonium (THPS) (so-called wet white leather), make the further tanning 4 hours of the 15% commercial mimosa extract powder ME that these skins stand to add gradually in computer-controlled dosage drum, keep its temperature simultaneously at 35 ℃.Measure its shrinkage temperature.The 3rd group (group C) with 15%Ecotan CSP tanning 60 minutes (pH4.0), then is increased to pH6.5 with sodium formiate and sodium bicarbonate with its pH gradually.Measure its shrinkage temperature according to the international leather technician chemist described method IUP 16 of association.The final shrinkage temperature of these leathers is as follows:
Handle the sample shrinkage temperature, ℃
Group A (Touch-me-notAction Plant) 76
Group B (THPS+ Touch-me-notAction Plant) 90
Group C (Ecotan CSP) 90
All these leathers by and the identical mode of commercial fat liquor (5%Chromopol UFBW+2%CoripolZXK+1%Chromopol SG, all products all are derived from the TFL of Germany), carry out emulsion oil-filling and by a standard method skinning.Find when watching evaluation that these leathers are having suitable difference aspect its outward appearance, feel and the color as naked eyes.With Touch-me-notAction Plant control tanning and pre-tanning of THPS and the then Touch-me-notAction Plant leather comparison of tanning again, the color of the leather of Ecotan CSP tanning is several to be white.Then, according to the dependence test method of international leather technician chemist association, measure all physical propertys of these leathers.Award table 16 and show to use successively between the resultant leather of THPS and Touch-me-notAction Plant and novel product Ecotan CSP that to the result in 22 sizable difference is arranged.
Table 16: handle sample CIELAB value without the color value (is that background records with the standard white ceramic tile) of the sheepskin leather of chromium institute tanning
L
*a
*b
*89.93 2.86 14.0 14.77 groups of C of 95.87-0.77 1.0 groups of 84.71 4.81 18.22 21.29 groups of B of A (Touch-me-notAction Plant) of Δ E white ceramic tile (THPS+ Touch-me-notAction Plant) (Ecotan CSP) 92.62 1.52 11.78 11.51
Table 17: the weight (g/sqft) without the sheep of chromium is handled example weight, gram/foot
2Group 74.27 groups of B of A (Touch-me-notAction Plant) (THPS+ Touch-me-notAction Plant) 60.00 groups of C (Ecotan CSP) 68.48
Table 18: the pliability without the sheep of chromium is handled sample pliability, BLC value
3.59 0.39 groups of C of 1.89 0.25 groups of B of average group A (Touch-me-notAction Plant) (THPS+ Touch-me-notAction Plant) (Ecotan CSP) 2.61 0.19
Table 19: handle the fracture of sample texture breaking weight (kg) texture without the texture strength of the sheep of chromium and prolong (mm)
19.3 2.8 9.6 0.4 groups of C of 34.3 8.5 8.7 0.7 groups of B of average average group A (Touch-me-notAction Plant) (THPS+ Touch-me-notAction Plant) (Ecotan CSP) 32.5 5.0 9.6 0.5
Table 20: the tear strength without the sheep of chromium is handled sample breaking weight (N) tear strength (N/mm)
44.7 8.8 30.0 4.5 groups of C of 74.1 11.2 51.8 3.6 groups of B of average average group A (Touch-me-notAction Plant) (THPS+ Touch-me-notAction Plant) (Ecotan CSP) 69.2 14.8 53.2 6.3
Table 21: handle sample breaking weight (N) tensile strength (N/mm without the tensile strength of the sheep of chromium
2)
118.2 20.5 7.7 0.9 groups of C of 306.3 83.8 20.4 3.5 groups of B of average average group A (Touch-me-notAction Plant) (THPS+ Touch-me-notAction Plant) (Ecotan CSP) 304.1 101.3 22.9 3.1
Table 22: the tension set without the sheep of chromium is handled sample tension set (%)
54.8 15.3 groups of C of 40.0 3.6 groups of B of average group A (Touch-me-notAction Plant) (THPS+ Touch-me-notAction Plant) (Ecotan CSP) 43.0 4.1
These data have been proved by using THPS and Touch-me-notAction Plant and the resulting leather of novel product EcotanCSP that sizable difference is arranged successively.
Embodiment 9
Synthesizing of this tanning compound is to carry out in 4 hours by 45 parts of commercial mimosa extract powder FS are reacted under 45-50 ℃ of also continuous the stirring with 40 parts of tetra methylol sulfuric acid phosphoniums and 15 parts of water.After this compound of indication will be represented with tanning compd E cotan CSP in this this preparation.
Make sheepskin (pH=1.6) degreasing of 12 immersions and regulate pH to 4.5.Then these skins arbitrarily are divided into two groups, every group contains 6 skins.First group (group A) keeps its temperature at 35 ℃ with 15% commercial mimosa extract powder ME tanning 4 hours in a computer-controlled dosage drum simultaneously.Measure its shrinkage temperature according to the international leather technician chemist described method IUP 16 of association.Then in this identical bath with 9.12% alkali formula al formate (1%Al
2O
3) these skins of tanning 1 hour again, the pH that will bathe with alkali this moment is adjusted to pH4.4-4.5 gradually.Measure its shrinkage temperature.Second group (group B) was with 15%Ecotan CSP tanning 60 minutes and make its pH be increased to pH6.5 gradually with sodium formiate and sodium bicarbonate.Measure its shrinkage temperature according to the international leather technician chemist described method IUP 16 of association.Then, according to being similar to the given method of group A, with 9.12% alkali formula al formate (1%Al
2O
3) these skins of tanning 1 hour again, the pH that will bathe with alkali this moment is adjusted to 4.4-4.5 gradually.Measure its shrinkage temperature.
To make all these leather emulsion oil-fillings, and to make it skinning by a standard method with the identical mode of commercial fat liquor (5%Chromopol UFBW+2%Coripol ZXK+1%Chromopol SG, all products are all available from German TFL).Measure the physical property of this skinning leather then according to the methods involving of international leather technician chemist association.Although these are from its final shrinkage temperature of leather identical (114 ℃) of group A and group B, its outward appearance, feel, weight (gram/foot 2) are different on the speciality with color.Leather with this novel tanning compound is softer significantly, and its color is lighter significantly.Table 23 given result in 29 shows by using in succession between Touch-me-notAction Plant and aluminium tanning agent and this novel product Ecotan CSP and the resulting leather of aluminium tanning agent quite big difference is arranged.
Table 23: handle sample CIELAB value without the color value (is that background records with the standard white ceramic tile) of chromium sheep
L
*a
*b
*Δ E white ceramic tile 68.84 7.14 11.93 30.24 groups of B of 95.87-0.77 1.0 groups of A (Touch-me-notAction Plant+aluminium) (Ecotan CSP+ aluminium) 82.68 1.7 9.2 15.76
Table 24: the weight (g/sqft) without the chromium sheep is handled example weight (gram/foot
2) group 68.48 groups of B of A (Touch-me-notAction Plant+aluminium) (Ecotan CSP+ aluminium) 67.48
Table 25: the pliability with the chromium sheep is handled sample pliability, BLC value
3.10 0.52 groups of B of average group A (Touch-me-notAction Plant+aluminium) (Ecotan CSP+ aluminium) 3.92 0.54
Table 26: handle the fracture of sample texture breaking weight (kg) texture without the texture strength of chromium sheep and prolong (mm)
29.8 6.0 9.2 0.5 groups of B of average average group A (Touch-me-notAction Plant+aluminium) (Ecotan CSP+ aluminium) 31.8 10.7 9.1 0.6
Table 27: the tear strength without the chromium sheep is handled sample breaking weight (N) tear strength (N/mm)
65.4 8.0 31.6 3.3 groups of B of average average group A (Touch-me-notAction Plant+aluminium) (Ecotan CSP+ aluminium) 60.3 11.7 32.7 3.7
Table 28: handle sample breaking weight (N) tensile strength (N/mm without the tensile strength of chromium sheep
2)
301.7 96.9 14.9 4.6 groups of B of average average group A (Touch-me-notAction Plant+aluminium) (Ecotan CSP+ aluminium) 237.1 59.0 13.5 4.0
Table 29: the tension set without the chromium sheep is handled sample tension set (%)
The content of 43.7 8.0 groups of B of average group A (Touch-me-notAction Plant+aluminium) (Ecotan CSP+ aluminium) 41.0 3.5 aluminium in exhausted is bathed is as follows: the content (pressing Al calculates) of handling sample aluminium (ppm) is organized 131.2 groups of B of A (Touch-me-notAction Plant+aluminium) (Ecotan CSP+ aluminium) 49.5
These results show, obtain having the leather satisfactory but characteristic that difference is quite big by this novel product and aluminium tanning agent.Particularly, better with the leather ratio of Ecotan CSP and the tanning of aluminium institute with the leather color and the pliability of Touch-me-notAction Plant and the tanning of aluminium institute.The content of aluminium is also inequality in the bath of used mistake, and is far better for novel cpd Ecotan CSP.
In the following example, embodiment 10 and 11 explanations prepare the method for tanning material according to the present invention.The application of tanning material in handling animal hides of embodiment 12,13 and 14 explanation embodiment 10 and 11.
Embodiment 10
In this embodiment, used De quaternary phosphonium compound is four (the methylol) Liu Suan Phosphonium (THPS) and the 75%w/w aqueous solution.Used vegetable tanning material is a Touch-me-notAction Plant.
The weight ratio of THPS and Touch-me-notAction Plant " activity " total amount is 1: 5.3 in this embodiment.
With THPS (75%w/w, 12.5g), Touch-me-notAction Plant (50g) and water (37.5g) is mixed in the sample container and places stove to be preheated to 80 ℃.
Just this sampling receptacle was shifted out in stove every 30 minutes and shake it, then put back in the stove again.Be 20 hours total heat-up time.
Regularly take a sample and do
31The P-NMR spectrum analysis.Its result awards following table 30.
Table 30
| Time | The Phosphonium product, area % | Residual THPS, area % |
| ????3 | ????64 | ????36 |
| ????5 | ????68 | ????32 |
| ????7 | ????77 | ????23 |
| ????8 | ????85 | ????15 |
| ????20 | ????100 | ????0 |
80 ℃ through 8 hours after, 85% THPS with Touch-me-notAction Plant reaction produce a kind of light red/brown viscous liquid.This product through 8 hours is a water soluble, but just reduces through its solubility after 20 hours.
Embodiment 11
In this embodiment, used De quaternary phosphonium compound is the condenses of a kind of THPS and urea (weight ratio of THPS and urea is 4: 1), can buy under registered trademark ALBRITE CS4.Used vegetable tanning material or Touch-me-notAction Plant.
In this embodiment, the weight ratio of it " activity " total amount of THPS and Touch-me-notAction Plant is 1: 5.
Be mixed in ALBRITE CS4 (12.5g), Touch-me-notAction Plant (50g) and water (37.5g) in the sample container and place stove to be preheated to 80 ℃.
Just this sampling receptacle was shifted out in stove every 30 minutes and shake it, then put back in the stove again.Be 8 hours total heat-up time.
After 8 hours, in stove, shift out, take a sample and do
31The P-NMR spectrum analysis.Its NMR stave is bright, and 85% complete polymerization De Phosphonium product and 15% unreacted THPS arranged.
Embodiment 12 to 14
These embodiment illustrate the application of the product of embodiment 1 and 2 as tanning agent.
Used leather tanning is as follows:
Comprise and the 50%w/w solution of a kind of sequestering agent (can buy) of amino three (methylene phosphonic acids) make the family expenses sheep rawhide (100g) of a collection of immersion and salt (8% weight) be floated to 200% to add 0.4% weight by registered trademark BRIQUEST 301-50A.Rotated this floating matter 20 minutes.The pH that learns this floating matter is 1.8.Thereafter the sodium formiate with 2.0% weight adds, and then rotates 30 minutes again, makes its pH can be adjusted to 3.6 to 3.8.
Add the tanning product (by 4% or 8% weight) of a kind of embodiment 10 or embodiment 11 and continue rotation 3 hours.Then, during whole 90 minutes, this floating matter was alkalized to pH6.0 by per 30 minutes.
Take out this skin, washed and emulsion oil-filling, measure shrinkage temperature according to its industry standard method of testing IUP 16 (SLP18) subsequently.
Its result is compared to following table 31:
Table 31
| Embodiment number | The tanning product | Consumption % | Shrinkage temperature (℃) * | Annotate |
| 3 | Embodiment 1 (20 hours) | Do not have | Do not have | The tanning product does not dissolve in floating matter |
| 4 | Embodiment 1 (8 hours) | ????4 ????8 | ????68 ????74 | O'clock formation red complex in pH＞4.8 |
| 5 | Embodiment 2 (8 hours) | ????4 ????8 | ????63 ????68 | The viscosity of tanning product is higher than embodiment 4 |
* the shrinkage temperature of rawhide of being untreated is 55 ℃.
The result of embodiment 13 and 14 (wherein red iron complex all is higher than formation in 4.8 o'clock at pH under two kinds of situations) comparison shows that, it is more remarkable than the tanning product (THP-urea/Touch-me-notAction Plant) that uses embodiment 11 to use the tanning product (THPS/ Touch-me-notAction Plant) of embodiment 10 to form complex compound.It is more remarkable than at consumption 4% time when the consumption 8% to form complex compound with each tanning product.
Claims (18)
1. a molecular formula is
Tanning material, wherein A is the tanning agent that contains polyphenol, and R
1, R
2And R
3Then be selected from-OH or X, X is muriate, vitriol or phosphoric acid salt here, and condition is R
1, R
2And R
3In have only one to be X.
2. the tanning material of claim 1, wherein X is muriate or vitriol.
3. claim 1 or 2 tanning material, wherein A is a vegetable tannages agent.
4. the tanning material of claim 3, tanning agent wherein comprises mimosa extract.
5. the tanning material of claim 3, wherein tanning agent comprises grain wood tannin extract, wattle extract, Caesalpinia spinosaKuntze collection, the sub-tannin extract in river or quebracho extract.
6. one kind provides claim 1 to 5 each the method for tanning material, and this method comprises, by from 35: 65 to 25: 75 weight ratio, 30 ℃ to 60 ℃ temperature, makes the same vegetable tannages agent reaction of a quaternary phosphonium compound 2 to 6 hours.
7. the method for claim 6 wherein by 1: 5 or bigger weight ratio, Ba Gai phosphonium compounds and vegetable tannages agent, randomly mixes in the presence of water, then makes this mixture reach 20 hours in 80 ℃ of heating of minimum temperature.
8. claim 6 or 7 method, wherein Gai quaternary phosphonium compound is four (methylol) Liu Suan Phosphonium or four (methylol) phosphonium chlorides.
9. claim 6 or 7 method, wherein Gai quaternary phosphonium compound comprises four (methylol) Liu Suan Phosphonium or the four (condensation products of a methylol) phosphonium chloride and an organic nitrogen compound.
10. the method for claim 9, wherein this organic nitrogen compound is urea, thiocarbamide or a kind of amine.
11. the method for claim 9 or 10, wherein Gai quaternary phosphonium compound comprises the four (condensation products of methylol) Liu Suan Phosphonium and urea.
12. each prepared tanning material of method by claim 6 to 11.
13. the application of the tanning material of claim 12 in handling animal hides.
14. according to the handled animal hides of claim 13.
15. the method for a tanning rawhide comprises that each tanning material of from 1 to 30% weight (based on the weight of this rawhide) claim 1 to 5 is handled this rawhide.
16. the method for claim 15, its pH be 2.5 to 8.5 and temperature be under 15 ℃ to 45 ℃ the condition, carried out 2 hours to 10 hours.
17. the method for claim 15 or 16 comprises that also a kind of concentration is the aluminium tanning agent of 0.1% to 5% (based on the weight of this rawhide).
18. the method for claim 17, wherein this aluminium tanning agent is aluminum chloride, Tai-Ace S 150, aluminum acetate or al formate.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NZ508114 | 2000-11-13 | ||
| NZ50811400 | 2000-11-13 | ||
| GB0105720.7 | 2001-03-08 | ||
| GB0105720A GB0105720D0 (en) | 2001-03-08 | 2001-03-08 | Tannages |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1474876A true CN1474876A (en) | 2004-02-11 |
Family
ID=26245798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA018187838A Pending CN1474876A (en) | 2000-11-13 | 2001-11-08 | Tannages and tanning material |
Country Status (6)
| Country | Link |
|---|---|
| CN (1) | CN1474876A (en) |
| AR (1) | AR031884A1 (en) |
| AU (1) | AU2002223788A1 (en) |
| GB (1) | GB2383049A (en) |
| TW (1) | TW541341B (en) |
| WO (1) | WO2002038813A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102016078B (en) * | 2008-04-01 | 2014-06-04 | 罗地亚管理公司 | Process for pre-tanning and tanning skins with organic tanning agent |
| CN104745736A (en) * | 2015-03-30 | 2015-07-01 | 陕西科技大学 | Graphene/aluminium oxide nano-composite tanning agent and preparation method thereof |
| CN104894302A (en) * | 2015-03-30 | 2015-09-09 | 陕西科技大学 | Graphene oxide/iron nanometer composite tanning agent and preparation method thereof |
| CN106755630A (en) * | 2017-01-09 | 2017-05-31 | 河北科技大学 | A kind of leather tanning method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR0204998A (en) * | 2002-12-09 | 2004-07-20 | Tanac S A | Process of modification of the physicochemical properties of a mimosa acacia plant extract, modified plant extract, and use of a chemically modified plant extract |
| US11725161B2 (en) * | 2018-11-16 | 2023-08-15 | Mitsubishi Gas Chemical Company, Inc. | Carboxylic acid ester compound, production method thereof, and fragrance composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2732278A (en) * | 1956-01-24 | Tanning with tetrakis- | ||
| DE1024675B (en) * | 1954-04-03 | 1958-02-20 | Bayer Ag | Process for the production of amphoterically modified tanning agents of vegetable origin |
| US3104151A (en) * | 1961-06-30 | 1963-09-17 | Windus Wallace | Combination tannage with tetrakis (hydroxy-methyl) phosphonium chloride and a phenol |
| CH691062A5 (en) * | 1996-06-17 | 2001-04-12 | Tfl Ledertechnik Gmbh & Co Kg | An aqueous composition for pre-tanning of hide pelts or retanning leather. |
-
2001
- 2001-11-08 AU AU2002223788A patent/AU2002223788A1/en not_active Abandoned
- 2001-11-08 CN CNA018187838A patent/CN1474876A/en active Pending
- 2001-11-08 WO PCT/GB2001/004939 patent/WO2002038813A1/en not_active Application Discontinuation
- 2001-11-08 GB GB0305948A patent/GB2383049A/en not_active Withdrawn
- 2001-11-13 AR ARP010105286A patent/AR031884A1/en unknown
- 2001-11-13 TW TW90128110A patent/TW541341B/en active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102016078B (en) * | 2008-04-01 | 2014-06-04 | 罗地亚管理公司 | Process for pre-tanning and tanning skins with organic tanning agent |
| CN104745736A (en) * | 2015-03-30 | 2015-07-01 | 陕西科技大学 | Graphene/aluminium oxide nano-composite tanning agent and preparation method thereof |
| CN104894302A (en) * | 2015-03-30 | 2015-09-09 | 陕西科技大学 | Graphene oxide/iron nanometer composite tanning agent and preparation method thereof |
| CN106755630A (en) * | 2017-01-09 | 2017-05-31 | 河北科技大学 | A kind of leather tanning method |
Also Published As
| Publication number | Publication date |
|---|---|
| TW541341B (en) | 2003-07-11 |
| GB0305948D0 (en) | 2003-04-23 |
| GB2383049A (en) | 2003-06-18 |
| AR031884A1 (en) | 2003-10-08 |
| AU2002223788A1 (en) | 2002-05-21 |
| WO2002038813A1 (en) | 2002-05-16 |
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