CN103194548B - A kind of Zirconium-aluminum-titanium tan waterproof garment leather and preparation method thereof - Google Patents
A kind of Zirconium-aluminum-titanium tan waterproof garment leather and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of zirconium aluminum titanium tannage waterproof garment leather and preparation method thereof, including pretreatment, tanning, retanning, dyeing, fatliquoring steps；Chrome-free, without phosphorus pollution in finished leather, formaldehydeless release, physical and mechanical properties is better than People's Republic of China's light industry industry standard clothing leather standard (QB/T 1,872 2004), tensile strength >=10N/mm2, elongation at break >=60%, tearing strength >=30/N/mm, burst apart height >=9mm；Leather-making mud can directly burn, and does not has potential Cr VI dangerous.The present invention can substitute traditional chrome tanning agent for tanning, coordinate tanning agent (ZA coordinates tanning agent), zirconium aluminum titanium to coordinate tanning agent (DMT I coordinates tanning agent) to replace chrome tanning agent with zirconium aluminum fatting agent is fixed simultaneously, eliminate chromic salts in production process and leatherware garbage and, to the mankind and the pollution of environment, open new approach for producing Chrome-free water proof type clothing leather.
Description
Technical field
The invention belongs to function leatherwork technology field, relate to Zirconium-aluminum-titanium and coordinate tanning technology and the waterproof garment leather manufacturing technology of tanning agent.
Background technology
In recent years, China's leather industry quickly grows, and has been developing progressively as the production of world's leather, processing and trade centre；Since 1883, since Dennis invention one bath chrome tanning, due to the combination property that chrome leather is good, chrome tanning agent became the main tanning agent of leather (light leather) tanning, almost without alternative；Along with development and the continuous progress of society in epoch, chrome tanning is the most faced with formidable challenges；On the one hand, chromium reserves in the world are limited and be non-renewable resources, and China is chromium depleted country, and substantial amounts of use can move towards the reality that exhaustion is difficult to avoid；On the other hand, the pollution of chromium of leather industry, have become as world's leather industry and realize the obstacle that sustainable development is impassable, be also the global problem that faced of leather industry.
In order to thoroughly solve the pollution problem of chromium, people turn to the research to chrome-free tanning agent and tannage sight, and have carried out substantial amounts of research and probe, such as aldehyde tannage, oil tanning, vegetable tanning, other metal tan and Chrome-free Combined tanning etc.；Regrettably, using the leather obtained by above-mentioned chrome-free tanning technology, its quality all cannot match in excellence or beauty with chrome leather；Thus, the existing application without chrome tanning is greatly limited, and this is also the basic reason place that chrome tanning dominant position in leather industry cannot be shaken always；-X tannage (X-represents the organic and inorganic tanning agent in addition to chromium) is planted in having of very being praised highly at present, but finds in actual applications, plants-X tannage and is generally not suitable for soft leather production.
Additionally, the clothing leather that existing chrome-free tanning agent is produced often occurs that whiteness is inadequate；Or there is not color inhibition；Or shrinkage temperature is the highest, it is unfavorable for following process and makes the problems such as habilimentation processing；It can be said that current chrome-free tanning agent and tanning technology thereof are the most ripe and perfect, it would be highly desirable to develop more advanced technology and matched auxiliary agent comes performance and the quality of improving product；Leather products develops towards the direction of ecology, personalization, functionalization, fashion-orientation and best quality, and for clothing leather and the functionalization of goods and the feature of environmental protection thereof, Zirconium-aluminum-titanium tan waterproof garment leather will be favored by consumer.
Summary of the invention
A kind of Zirconium-aluminum-titanium that it is an object of the invention to provide for the deficiencies in the prior art coordinates tanning agent tanning technology, the leather that institute's tan obtains does not contains chromium, also without chromium in waste tanning liquor, thus eliminate the pollution of heavy metal chromium, be characterized in Zirconium-aluminum-titanium tan waterproof garment leather shrinkage temperature up to more than 90 DEG C, finished leather is soft, plentiful, shelf-stable, Chrome-free, without phosphorus pollution, formaldehydeless release；Finished leather static water absorption rate is less than 20%；Pure white being suitable for of leather body is cooked white leather, and finished leather has excellent physical-mechanical property, is better than People's Republic of China's light industry industry standard clothing leather standard (QB/T 1872-2004), it is simple to following process and making habilimentation processing；Leather-making mud can directly burn or fill, and does not has potential hexavalent chromium polluted risk.
The present invention is adopted the technical scheme that for achieving the above object:
Zirconium-aluminum-titanium tan waterproof garment leather and preparation method thereof, comprises the following steps, raw materials by weight portion meter wherein used:
(1) pretreatment: label taking standard softens the pelt after pickling, weighs, is placed in suspension type wood rotary drum, hide increases weight to 150% ~ 200%, and in rotary drum, the pelt meter after weightening finish is heavily 100 parts；Under room temperature, add acid solution 50 ~ 150 parts, add pretreating agent DMT-I and coordinate tanning agent or ZA to coordinate tanning agent 0.5 ~ 2.5 part in rotary drum, rotate 10 ~ 50min, stop drum；
(2) tanning: open drum door, the DMT-II adding 7 ~ 20 parts from drum door coordinates tanning agent, rotates 120 ~ 240min continuously；Adding the sodium formate solution (1:10 water dissolution) of 1 ~ 3 part of prior dissolving from drum gudgeon, rotate 10 ~ 50min, then carry alkali with the sodium bicarbonate (1:10 water dissolution) of 2 ~ 5 parts, adjusting pH is 3.7 ~ 4.2；The last hot water 100 ~ 200 parts adding 50 ~ 60 DEG C from drum gudgeon, makes the temperature of body lotion in rotary drum rise to 40 ~ 45 DEG C, rotates 120 ~ 240min continuously；Stand overnight, after rotating 30min next day, go out drum, stand 2 days；
(3) water squeezing: utilize by formula wringing machine water squeezing, take the circumstances into consideration to squeeze 1 ~ 2 time depending on crust leather moisture；Require: crust leather moisture 50% ~ 55%；
(4) shaving: shaving thickness 0.4 ~ 0.6mm (monolayer)；
(5) weigh: correct amount, as the meter material foundation of following operation；
(6) rinsing: 200 ~ 300 parts of water, temperature: 32 ~ 35 DEG C, from drum gudgeon, add peregal 0.1 ~ 0.5 part, 0.1 ~ 0.5 part of formic acid, rotate 60min, discharge opeing；
(7) neutralizing: 100 ~ 150 parts of water, temperature: 32 ~ 35 DEG C, add 0.5 ~ 1.5 part of sodium bicarbonate, 0.5 ~ 1.5 part of neutralizing retanning agent, rotate 30min from drum gudgeon, adjusting pH value is 4.5 ~ 5.0；
(8) retanning: 100 ~ 150 parts of water, temperature: 32 ~ 35 DEG C, from drum gudgeon, add 1 ~ 3 part of sulfonation artificial oil fatting agent JM, rotate 30min, add 1 ~ 3 part of DMT-II and coordinate tanning agent, rotate 90min；Add 0.5 ~ 2.0 part of acrylic resin retanning agent ART-4, rotate 30min, add 1 ~ 3 part of maleic anhydride retanning agent, rotate 40min；Add 0.5 ~ 1.5 part of formic acid, adjust pH=4.0, rotate 20min；
(9) secondary neutralizes: 100 ~ 150 parts of water, temperature: 32 ~ 35 DEG C, adds 0.5 ~ 1.5 part of sodium formate, 1.0 ~ 1.5 parts of sodium hyposulfite, rotates 40min, add 1 ~ 2 part of sodium bicarbonate, adjust pH5.5 ~ 6.0, rotate 120 ~ 240min, discharge opeing from drum gudgeon；
(10) washing: flowing water washes 10min, discharge opeing；
(11) dyeing and fat-liquoring: 100 ~ 150 parts of water, temperature: 45 ~ 55 DEG C, from drum gudgeon, add 2.0 ~ 2.5 parts of black acid dye, rotate 60min, add 2 ~ 6 parts of silicone waterproof currying agents, 1 ~ 4 part of Organic fluoride class waterproofing agent, rotate 90min, add 0.5 ~ 1.5 part of formic acid, rotate 20min, add 1 ~ 5 part of Zirconium-aluminum-titanium and coordinate tanning agent (DMT-I coordinates tanning agent) or 1 ~ 5 part of zirconium-aluminum to coordinate tanning agent (ZA joins and tanning agent), be fixed, adjust pH=4.0, rotate 40min；
(12) washing: 200 ~ 400 parts of water, temperature: room temperature, rotate 15min, discharge opeing；
(13) routinely technique carry out water squeezing stretching, extension, be dried, moisture regain, toggling, fall soft；
In tanning step:
Described Chrome-free multi-metal complex tanning agent, it is the metal composite tanning agent based on zirconates and aluminium salt；The consumption of described Chrome-free multi-metal complex tanning agent is preferably 12 ~ 15 parts.
In the present invention:
Described ZA zirconium-aluminum coordinates tanning agent and DMT-I Zirconium-aluminum-titanium to coordinate tanning agent, and DMT-II Zirconium-aluminum-titanium coordinates tanning agent to be based on zirconates and aluminium salt, and a kind of non-chromium formed by adding multiple auxiliary agent coordinates tanning agent；Its technical specification is as follows:
(1) outward appearance: white powder；
(2) dissolubility: 30 ~ 50g/100g water (25 DEG C)；
(3) charge property (10% aqueous solution): electropositivity；
(3) pH (10% aqueous solution): 1.0 ~ 3.2；
(4) oxide content: 15% ~ 30%(w/w)；
(5) granularity: 70 ~ 200 mesh；
ZA used coordinates tanning agent, DMT-I to coordinate tanning agent and DMT-II to coordinate tanning agent produced by Chengdu Bailejin Biological Scinece & Technology Co., Ltd. and provide, and other chemical materialss are commercially available technical grade chemicals.
Another technical scheme of the present invention is a kind of double waterproof chromium-free tanned sheep fur and its making prepared by said method, it is characterised in that its index met is as follows:
(1) according to the People's Republic of China (PRC) " clothing leather light industry standard " (QB/T3812.9-1999) " mensuration of leather shrinking temperature ", mensuration shrinkage temperature, up to more than 90 DEG C, deposits not tempering for a long time；
(2) according to People's Republic of China (PRC) QB/T 1275-1991 " mensuration of leather products-chromic oxide ", this clothing leather product is measured without chromium；
(3) People's Republic of China's light industry standard QB/T 1269-1991 " mensuration of leather products-percentage elongation ", measures tensile strength >=10N/mm2, elongation at break >=60%；
(4) according to National Standard of the People's Republic of China GB/T 4689.21-2008 " leather-physics and the test of mechanical test-static water absorption ", the static water absorption amount measuring clothing leather only has about 20%.
Detailed description of the invention:
Below by embodiment, the present invention is specifically described; it is served only for the present invention is further described; it is not intended that limiting the scope of the present invention, the present invention can be made improvement and the adjustment of some non-intrinsically safes by the technician in this field according to the content of foregoing invention.
Embodiment
1
:
(1) pretreatment: label taking standard softens the pelt after pickling, weighs, is placed in suspension type wood rotary drum, hide increases weight to 150% ~ 200%, and in rotary drum, the pelt meter after weightening finish is heavily 100 parts；Under room temperature, add acid solution 50 parts, add pretreating agent DMT-I and coordinate tanning agent or ZA to coordinate tanning agent 1 part in rotary drum, rotate 20min, stop drum；
(2) tanning: open drum door, the DMT-II adding 7 parts from drum door coordinates tanning agent (Zirconium-aluminum-titanium coordinates tanning agent DMT-II, Chengdu Bailejin Biological Scinece & Technology Co., Ltd., batch number: 2012-05-08), rotates 120min continuously；Adding the sodium formate solution (1:10 water dissolution) of 1 part of prior dissolving from drum gudgeon, rotate 10min, then carry alkali with the sodium bicarbonate (1:10 water dissolution) of 3.5 parts, adjusting pH is 3.7 ~ 4.2；The last hot water 100 parts adding 50 ~ 60 DEG C from drum gudgeon, makes the temperature of body lotion in rotary drum rise to 40 ~ 45 DEG C, rotates 120min continuously；Stand overnight, after rotating 30min next day, go out drum, stand 2 days；
(3) water squeezing: utilize by formula wringing machine water squeezing, take the circumstances into consideration to squeeze 1 ~ 2 time depending on crust leather moisture；Require: crust leather moisture 50% ~ 55%；
(4) shaving: shaving thickness 0.4 ~ 0.6mm (monolayer)；
(5) weigh: correct amount, as the meter material foundation of following operation；
(6) rinsing: 200 parts of water, temperature: 32 ~ 35 DEG C, from drum gudgeon, add peregal 0.2 part, 0.2 part of formic acid, rotate 60min, discharge opeing；
(7) neutralizing: 100 ~ 150 parts of water, temperature: 32 ~ 35 DEG C, add 1.0 parts of sodium bicarbonate, 1.0 parts of neutralizing retanning agents, rotate 30min from drum gudgeon, adjusting pH value is 4.5 ~ 5.0；
(8) retanning: 100 ~ 150 parts of water, temperature: 32 ~ 35 DEG C, 2 parts of sulfonation artificial oil fatting agent JM are added from drum gudgeon, rotate 30min, add 2 parts of DMT-II and coordinate tanning agent (Zirconium-aluminum-titanium cooperation tanning agent DMT-II, Chengdu Bailejin Biological Scinece & Technology Co., Ltd., batch number: 2012-05-08), rotate 90min；Add chemical plant, 1.0 parts of acrylic resin retanning agent ART-4(Xinhui of Guangdong Province), rotate 30min, add 2 parts of maleic anhydride retanning agents (BSF(China) Chemical Co., Ltd.), rotate 40min；Add 1.0 parts of formic acid, adjust pH=4.0, rotate 20min；
(9) secondary neutralizes: 100 ~ 150 parts of water, temperature: 32 ~ 35 DEG C, adds 0.8 part of sodium formate, 1.2 parts of sodium hyposulfite, rotates 40min, add 1.5 parts of sodium bicarbonate, adjust pH5.5 ~ 6.0, rotate 120min, discharge opeing from drum gudgeon；
(10) washing: flowing water washes 10min, discharge opeing；
null(11) dyeing and fat-liquoring: 100 ~ 150 parts of water，Temperature: 45 ~ 55 DEG C，2.0 parts of black acid dye are added from drum gudgeon，Rotate 60min，Add 2 parts of silicone waterproof currying agent Densodrin CD(waterproof currying agent Densodrin CD，BASF joint-stock company of Germany，Batch number: 2012-04-21)，4 parts of Organic fluoride class waterproofing agent Densodrin OF(waterproof currying agent Densodrin OF，BASF joint-stock company of Germany，Batch number: 2012-04-21)，Rotate 90min，Add 0.8 part of formic acid，Rotate 20min，(DMT-I coordinates tanning agent to add 3 parts of Zirconium-aluminum-titaniums cooperation tanning agents，Chengdu Bailejin Biological Scinece & Technology Co., Ltd.,Batch number) it is fixed，Adjust pH=4.0，Rotate 40min；
(12) washing: 200 ~ 400 parts of water, temperature: room temperature, rotate 15min, discharge opeing；
(13) routinely technique carry out water squeezing stretching, extension, be dried, moisture regain, toggling, fall soft.
Embodiment
2
:
(1) pretreatment: label taking standard softens the pelt after pickling, weighs, is placed in suspension type wood rotary drum, hide increases weight to 150% ~ 200%, and in rotary drum, the pelt meter after weightening finish is heavily 100 parts；Under room temperature, add acid solution 50 parts, add pretreating agent DMT-I and coordinate tanning agent or ZA to coordinate tanning agent 0.5 part in rotary drum, rotate 20min, stop drum；
(2) tanning: open drum door, the DMT-II adding 10 parts from drum door coordinates tanning agent (Zirconium-aluminum-titanium coordinates tanning agent DMT-II, Chengdu Bailejin Biological Scinece & Technology Co., Ltd., batch number: 2012-05-08), rotates 120min continuously；Adding the sodium formate solution (1:10 water dissolution) of 1 part of prior dissolving from drum gudgeon, rotate 10min, then carry alkali with the sodium bicarbonate (1:10 water dissolution) of 2 parts, adjusting pH is 3.7 ~ 4.2；The last hot water 100 parts adding 50 ~ 60 DEG C from drum gudgeon, makes the temperature of body lotion in rotary drum rise to 40 ~ 45 DEG C, rotates 120min continuously；Stand overnight, after rotating 30min next day, go out drum, stand 2 days；
(3) water squeezing: utilize by formula wringing machine water squeezing, take the circumstances into consideration to squeeze 1 ~ 2 time depending on crust leather moisture；Require: crust leather moisture 50% ~ 55%；
(4) shaving: shaving thickness 0.4 ~ 0.6mm (monolayer)；
(5) weigh: correct amount, as the meter material foundation of following operation；
(6) rinsing: 200 parts of water, temperature: 32 ~ 35 DEG C, from drum gudgeon, add peregal 0.2 part, 0.1 part of formic acid, rotate 60min, discharge opeing；
(7) neutralizing: 100 ~ 150 parts of water, temperature: 32 ~ 35 DEG C, add 1.0 parts of sodium bicarbonate, 1.0 parts of neutralizing retanning agents, rotate 30min from drum gudgeon, adjusting pH value is 4.5 ~ 5.0；
(8) retanning: 100 ~ 150 parts of water, temperature: 32 ~ 35 DEG C, 1 part of sulfonation artificial oil fatting agent JM is added from drum gudgeon, rotate 30min, add 1 part of DMT-II and coordinate tanning agent (Zirconium-aluminum-titanium cooperation tanning agent DMT-II, Chengdu Bailejin Biological Scinece & Technology Co., Ltd., batch number: 2012-05-08), rotate 90min；Add chemical plant, 0.5 part of acrylic resin retanning agent ART-4(Xinhui of Guangdong Province), rotate 30min, add 1 part of maleic anhydride retanning agent (BSF(China) Chemical Co., Ltd.), rotate 40min；Add 1 part of formic acid, adjust pH=4.0, rotate 20min；
(9) secondary neutralizes: 100 ~ 150 parts of water, temperature: 32 ~ 35 DEG C, adds 0.5 part of sodium formate, 1.0 parts of sodium hyposulfite, rotates 40min, add 2.0 parts of sodium bicarbonate, adjust pH5.5 ~ 6.0, rotate 120min, discharge opeing from drum gudgeon；
(10) washing: flowing water washes 10min, discharge opeing；
null(11) dyeing and fat-liquoring: 100 ~ 150 parts of water，Temperature: 45 ~ 55 DEG C，2.0 parts of black acid dye are added from drum gudgeon，Rotate 60min，Add 4 parts of silicone waterproof currying agent Densodrin CD(waterproof currying agent Densodrin CD，BASF joint-stock company of Germany，Batch number: 2012-04-21)，2 parts of Organic fluoride class waterproofing agent Densodrin OF(waterproof currying agent Densodrin OF，BASF joint-stock company of Germany，Batch number: 2012-04-21)，Rotate 90min，Add 0.8 part of formic acid，Rotate 20min，(ZA joins and tanning agent to coordinate tanning agent with 3 parts of zirconiums-aluminum，Chengdu Bailejin Biological Scinece & Technology Co., Ltd.) it is fixed，Adjust pH=4.0，Rotate 40min；
(12) washing: 200 ~ 400 parts of water, temperature: room temperature, rotate 15min, discharge opeing；
(13) routinely technique carry out water squeezing stretching, extension, be dried, moisture regain, toggling, fall soft.
Embodiment
3
:
(1) pretreatment: the pelt after label taking standard softens pickling is weighed, and is placed in suspension type wood rotary drum, hide increases weight to 150% ~ 200%, and in rotary drum, the pelt meter after weightening finish is heavily 100 parts；Under room temperature, add acid solution 50 parts, add pretreating agent DMT-I and coordinate tanning agent or ZA to coordinate tanning agent 2 parts in rotary drum, rotate 20min, stop drum；
(2) tanning: open drum door, the DMT-II adding 15 parts from drum door coordinates tanning agent (Zirconium-aluminum-titanium coordinates tanning agent DMT-II, Chengdu Bailejin Biological Scinece & Technology Co., Ltd., batch number: 2012-05-08), rotates 120min continuously；Adding the sodium formate solution (1:10 water dissolution) of 1 part of prior dissolving from drum gudgeon, rotate 10min, then carry alkali with the sodium bicarbonate (1:10 water dissolution) of 4 parts, adjusting pH is 3.7 ~ 4.2；The last hot water 100 parts adding 50 ~ 60 DEG C from drum gudgeon, makes the temperature of body lotion in rotary drum rise to 40 ~ 45 DEG C, rotates 120min continuously；Stand overnight, after rotating 30min next day, go out drum, stand 2 days；
(3) water squeezing: utilize by formula wringing machine water squeezing, take the circumstances into consideration to squeeze 1 ~ 2 time depending on crust leather moisture；Require: crust leather moisture 50% ~ 55%；
(4) shaving: shaving thickness 0.4 ~ 0.6mm (monolayer)；
(5) weigh: correct amount, as the meter material foundation of following operation；
(6) rinsing: 200 parts of water, temperature: 32 ~ 35 DEG C, from drum gudgeon, add peregal 0.2 part, 0.2 part of formic acid, rotate 60min, discharge opeing；
(7) neutralizing: 100 ~ 150 parts of water, temperature: 32 ~ 35 DEG C, add 1.0 parts of sodium bicarbonate, 1.0 parts of neutralizing retanning agents, rotate 30min from drum gudgeon, adjusting pH value is 4.5 ~ 5.0；
(8) retanning: 100 ~ 150 parts of water, temperature: 32 ~ 35 DEG C, 3 parts of sulfonation artificial oil fatting agent JM are added from drum gudgeon, rotate 30min, add 3 parts of DMT-II and coordinate tanning agent (Zirconium-aluminum-titanium cooperation tanning agent DMT-II, Chengdu Bailejin Biological Scinece & Technology Co., Ltd., batch number: 2012-05-08), rotate 90min；Add chemical plant, 1.0 parts of acrylic resin retanning agent ART-4(Xinhui of Guangdong Province), rotate 30min, add 1 part of maleic anhydride retanning agent (BSF(China) Chemical Co., Ltd.), rotate 40min；Add 0.8 part of formic acid, adjust pH=4.0, rotate 20min；
(9) secondary neutralizes: 100 ~ 150 parts of water, temperature: 32 ~ 35 DEG C, adds 1.5 parts of sodium formates, 1.0 parts of sodium hyposulfite, rotates 40min, add 1 part of sodium bicarbonate, adjust pH5.5 ~ 6.0, rotate 120min, discharge opeing from drum gudgeon；
(10) washing: flowing water washes 10min, discharge opeing；
null(11) dyeing and fat-liquoring: 100 ~ 150 parts of water，Temperature: 45 ~ 55 DEG C，2.0 parts of black acid dye are added from drum gudgeon，Rotate 60min，Add 6 parts of silicone waterproof currying agent Densodrin CD(waterproof currying agent Densodrin CD，BASF joint-stock company of Germany，Batch number: 2012-04-21)，1 part of Organic fluoride class waterproofing agent Densodrin OF(waterproof currying agent Densodrin OF，BASF joint-stock company of Germany，Batch number: 2012-04-21)，Rotate 90min，Add 0.8 part of formic acid，Rotate 20min，(DMT-I coordinates tanning agent to add 5 parts of Zirconium-aluminum-titaniums cooperation tanning agents，Chengdu Bailejin Biological Scinece & Technology Co., Ltd.,Batch number) it is fixed，Adjust pH=4.0，Rotate 40min；
(12) washing: 200 ~ 400 parts of water, temperature: room temperature, rotate 15min, discharge opeing；
(13) routinely technique carry out water squeezing stretching, extension, be dried, moisture regain, toggling, fall soft.
Claims (1)
1. the manufacture method of a Zirconium-aluminum-titanium tan waterproof garment leather, it is characterised in that comprising the following steps, wherein material therefor is counted the most by weight:
(1) pretreatment: label taking standard softens the pelt after pickling, weighs, is placed in suspension type wood rotary drum, hide increases weight to 150%～200%, rotary drum
Pelt meter after interior weightening finish is heavily 100 parts；Under room temperature, addition acid solution 50～150 parts, add pretreating agent DMT-I Zirconium-aluminum-titanium and coordinate tanning agent
Or ZA zirconium-aluminum coordinates tanning agent 0.5～2.5 parts in rotary drum, rotates 10～50min, stops drum；
(2) tanning: open drum door, the DMT-II adding 7～20 parts from drum door coordinates tanning agent, rotates 120～240min continuously；From drum gudgeon
Middle addition 1～3 parts of prior 1: 10 water-soluble sodium formate solution, rotate 10～50min, then 1: 10 water-soluble little with 2～5 parts
Soda carries alkali, and adjusting pH is 3.7～4.2；The last hot water 100 adding 50～60 DEG C from drum gudgeon～200 parts, make body lotion in rotary drum
Temperature rises to 40～45 DEG C, rotates 120～240min continuously；Stand overnight, after rotating 30min next day, go out drum, stand 2 days；
(3) water squeezing: utilize by formula wringing machine water squeezing, take the circumstances into consideration to squeeze 1～2 time depending on crust leather moisture；Require: crust leather moisture 50%～55%；
(4) shaving: monolayer shaving thickness 0.4～0.6mm；
(5) weigh: correct amount, as the meter material foundation of following operation；
(6) rinsing: water 200～300 parts, temperature: 32～35 DEG C, from drum gudgeon, add peregal 0.1～0.5 part, formic acid 0.1～0.5 part,
Rotate 60min, discharge opeing；
(7) neutralizing: water 100～150 parts, temperature: 32～35 DEG C, add 0.5～1.5 part of sodium bicarbonate from drum gudgeon, 0.5～1.5 part neutralizes multiple
Tanning agent, rotates 30min, and adjusting pH value is 4.5～5.0；
(8) retanning: water 100～150 parts, temperature: 32～35 DEG C, from drum gudgeon, add 1～3 part of sulfonation artificial oil fatting agent JM, rotate 30min,
Add 1～3 part of DMT-II and coordinate tanning agent, rotate 90min；Add 0.5～2.0 part of acrylic resin retanning agent ART-4, rotate 30min,
Add 1～3 part of maleic anhydride retanning agent, rotate 40min；Add 0.5～1.5 part of formic acid, adjust pH=4.0, rotate 20min；
(9) secondary neutralizes: water 100～150 parts, temperature: 32～35 DEG C, adds 0.5～1.5 part of sodium formate from drum gudgeon, and 1.0～1.5 parts big
Soda, rotates 40min, adds 1～2 part of sodium bicarbonate, adjusts pH5.5～6.0, rotates 120～240min, discharge opeing；
(10) washing: flowing water washes 10min, discharge opeing；
(11) dyeing and fat-liquoring: water 100～150 parts, temperature: 45～55 DEG C, from drum gudgeon, add 2.0～2.5 parts of black acid dye, rotate 60min,
Add 2～6 parts of silicone waterproof currying agents, 1～4 part of Organic fluoride class waterproofing agent, rotate 90min, add 0.5～1.5 part of formic acid, rotate
20min, adds 1～5 part of DMT-I Zirconium-aluminum-titanium and coordinates tanning agent or 1～5 part of ZA zirconium-aluminum to coordinate tanning agent, be fixed, adjust pH=4.0,
Rotate 40min；
(12) washing: water 200～400 parts, temperature: room temperature, rotate 15min, discharge opeing；
(13) routinely technique carry out water squeezing stretching, extension, be dried, moisture regain, toggling, fall soft；
Shrinkage temperature >=90 DEG C of obtained Zirconium-aluminum-titanium tan waterproof garment leather；Tensile strength >=10N/mm2, elongation at break >=60%, tear is strong
Degree >=30N/mm, burst apart height >=9mm；Leather static water absorption amount is less than 20%；Without trivalent chromium, Cr VI in leather；Leather organoleptic properties and reason
Change performance store 2 years maintained above constant；
Wherein, described standard softens pickling and comprises the steps: that raw material is the one in liming Corii Bovis seu Bubali, Corii Sus domestica or Corii Caprae seu Ovis after cuing open layer, thickness 2.0～
3.0mm, liming skin poidometer is heavily 100 parts；
A washes: water 100%, temperature: 37 DEG C, rotates 15min, discharge opeing；
B deliming: water 100%, 2 parts reach Willie card DLA without ammonia deliming agent, 1 part of lactic acid, rotation 30min, rotating speed 16rpm
C softens: add the compound enzyme F of 0.2 part, rotates 60min, rotating speed 16rpm, discharge opeing；
D washes: water 100%, room temperature, rotates 15min, discharge opeing；
E pickling: water 50%, temperature: room temperature；Open drum door, from drum gudgeon, add 7 parts of industrial table salts, rotate 10min, then from rotary drum
Axis hole adds 0.8 part of the formic acid dissolving 1: 20 water dissolution dilution completely in advance, rotates 30min, from drum gudgeon, add 1: 20 water
1.2 parts of the sulphuric acid of dissolved dilution, makes pH=2.6～2.8, rotates 120min.
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| CN201310139057.5A CN103194548B (en) | 2013-04-22 | 2013-04-22 | A kind of Zirconium-aluminum-titanium tan waterproof garment leather and preparation method thereof |
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| CN104988250B (en) * | 2015-06-23 | 2017-09-29 | 兴业皮革科技股份有限公司 | A kind of cattle hide upper leather less chrome tannage method based on zirconium aluminium titanium cooperation tanning agent |
| CN105671221B (en) * | 2015-07-08 | 2018-05-04 | 四川大学 | Double waterproof layer cattle hide upper leathers and preparation method thereof |
| CN105155307B (en) * | 2015-08-27 | 2018-08-28 | 兴业皮革科技股份有限公司 | A kind of leather hygrometric state dyeing and finishing color-fixing method based on zirconium aluminium titanium complex |
| CN105349710B (en) * | 2015-12-17 | 2018-07-10 | 湖南科技职业学院 | A kind of method of ox-hide Chrome-free combination tanning |
| CN105544249A (en) * | 2016-01-29 | 2016-05-04 | 佛山市聚成生化技术研发有限公司 | Dyeing method of pig leather |
| CN105994000B (en) * | 2016-05-24 | 2019-08-20 | 辽宁富新新材料有限公司 | A kind of dog chew and preparation method thereof |
| CN106282439B (en) * | 2016-09-22 | 2018-04-20 | 湖南永霏特种防护用品有限公司 | A kind of water-fastness, environment-friendly type clothing leather processing technology |
| CN116287487B (en) * | 2023-02-06 | 2024-02-06 | 珍寿实业(商丘)有限公司 | Preparation method of waterproof sheep vamp leather based on high-performance polymer material |
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| CN102206717A (en) * | 2011-05-04 | 2011-10-05 | 四川大学 | Method for preparing zirconium-aluminum multi-metal tanning liquor |
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| CN102787181A (en) * | 2012-08-01 | 2012-11-21 | 四川大学 | Zirconium-aluminum-titanium complex tanning agent based less-chrome tanning method |
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| CN102206717A (en) * | 2011-05-04 | 2011-10-05 | 四川大学 | Method for preparing zirconium-aluminum multi-metal tanning liquor |
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