CN103194548A - Zirconium-aluminum-titanium tannage waterproof clothing leather and making method thereof - Google Patents
Zirconium-aluminum-titanium tannage waterproof clothing leather and making method thereof Download PDFInfo
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Abstract
The invention discloses a zirconium-aluminum-titanium tannage waterproof clothing leather and a making method thereof. The making method comprises the steps of pretreatment, tanning, retanning, dyeing and fat-liquoring; the finished leather has no chrome-phosphor pollution and no formaldehyde emission, and the physical and mechanical performance of the finished leather is superior to the regulations of the Clothing Leather Standard of the Light Industry Standards of the PRC (QB/T1872-2004), the tensile strength is equal to or more than 10 N/mm<2>, the elongation at break is equal to or more than 60 percent, the tearing strength is equal to or more than 30/N/mm, and the bursting height is equal to or more than 9 mm; tannery sludge can be directly incinerated without potential risk of hexavalent chromium. The zirconium-aluminum-titanium tannage waterproof clothing leather can replace the traditional chrome tanning agent for tanning, a chrome-aluminum compound tanning agent (ZA compound tanning agent) and a chrome-aluminum-titanium compound tanning agent (DMT-I compound tanning agent) are used to replace the chrome tanning agent so as to fix a fatting agent, so the pollution of chromic salts in the leather product waste and during production to human being and environments is eliminated, and the zirconium-aluminum-titanium tannage waterproof clothing leather and the making method thereof open up a new approach for the production of chrome-free waterproof clothing leather.
Description
Technical field
The invention belongs to function leatherwork technology field, relate to tanning technology and waterproof garment leather manufacturing technology that Zirconium-aluminum-titanium cooperates tanning agent.
Background technology
In recent years, China's leather industry development develops into world's leather production, processing and trade center rapidly gradually; Since 1883, Dennis invention one was bathed since the chromic tanning, because the chrome tanned leather good comprehensive performances, chrome tanning agent becomes the main tanning agent of leather (light leather) tanning, almost can not be substituted; Along with the continuous progress of development of times and society, chromic tanning also is faced with formidable challenges; On the one hand, chromium reserves in the world is limited and be Nonrenewable resources, and China is poor chromium country, and it is the reality that is difficult to avoid that a large amount of uses can be moved towards exhaustion; On the other hand, the pollution of chromium of tanning industry has become world's tanning industry and has realized the impassable obstacle of Sustainable development, also is the global problem that tanning industry faces.
In order thoroughly to solve the pollution problem of chromium, people turn to research to chrome-free tanning agent and tannage to sight, and have carried out a large amount of research and explored, as aldehyde tannage, oil tanning, vegetable tanning, other metal tan and Chrome-free in conjunction with tanning etc.; Regrettably, adopt the prepared leather of above-mentioned chrome-free tanning technology, its quality all can't match in excellence or beauty with chrome tanned leather; Thereby the application of existing no chromic tanning is greatly limited, and this also is the basic reason place that the dominant position of chromic tanning in tanning industry can't be shaken always; Having of very being praised highly at present planted-X tannage (X-represent the organic and inorganic tanning agent outside the dechromisation), but discovery in actual applications, plant-the X tannage generally is not suitable for soft leather production.
In addition, whiteness often to occur not enough for the clothing leather produced of existing chrome-free tanning agent; Perhaps there is not anti-xanthochromia; Perhaps shrinkage temperature is not high, is unfavorable for problems such as following process and the processing of making habilimentation; We can say that present chrome-free tanning agent and tanning technology thereof are ripe not enough and perfect, demand urgently developing modern technique more and with it supporting auxiliary agent promote performance and the quality of product; Leather products develops towards the direction of ecology, personalization, functionalization, fashion-orientation and best quality, and with regard to the functionalization and the feature of environmental protection of clothing leather and goods thereof, tan waterproof garment leather of Zirconium-aluminum-titanium will be subjected to human consumer's favor.
Summary of the invention
A kind of Zirconium-aluminum-titanium that the objective of the invention is to provide at the deficiencies in the prior art cooperates tanning agent tanning technology, the leather of tanning does not contain chromium, do not contain chromium in the tanning waste liquid yet, thereby eliminated the pollution of heavy metal chromium, be characterized in that the Zirconium-aluminum-titanium waterproof garment leather shrinkage temperature of tanning can reach more than 90 ℃ finished leather softness, plentiful, anti-storage, Chrome-free, without phosphorus pollution, formaldehydeless release; The static water-intake rate of finished leather is lower than 20%; The leather body is pure white to be fit to do white leather, and finished leather has good physical-mechanical property, is better than People's Republic of China's light industry industry standard clothes with leather standard (QB/T 1872-2004), is convenient to following process and makes habilimentation processing; Leather-making mud can directly burn or landfill, does not have potential hexavalent chromium polluted risk.
The technical scheme that the present invention takes for achieving the above object is:
The Zirconium-aluminum-titanium waterproof garment leather and preparation method thereof of tanning may further comprise the steps, wherein used raw materials by weight portion meter:
(1) pre-treatment: the pelt after the softening pickling of the standard of getting, weigh, place in the suspension type wood rotary drum, hide increases weight to 150% ~ 200%, and the pelt meter in the rotary drum after the weightening finish heavily is 100 parts; Under the normal temperature, add 50 ~ 150 parts of acid solutions, add pretreating agent DMT-I and cooperate tanning agent or ZA to cooperate 0.5 ~ 2.5 part of tanning agent in rotary drum, rotate 10 ~ 50min, stop drum;
(2) tanning: open drum door, the DMT-II that adds 7 ~ 20 parts from drum door cooperates tanning agent, rotates 120 ~ 240min continuously; Add 1 ~ 3 part of sodium formate solution (1:10 water dissolution) of dissolving in advance from drum gudgeon, rotate 10 ~ 50min, use 2 ~ 5 parts sodium bicarbonate (1:10 water dissolution) to carry alkali then, adjusting pH is 3.7 ~ 4.2; 100 ~ 200 parts of hot water that add 50 ~ 60 ℃ at last from drum gudgeon make the temperature of body lotion in the rotary drum rise to 40 ~ 45 ℃, rotate 120 ~ 240min continuously; Standing over night goes out drum after rotating 30min next day, leaves standstill 2 days;
(3) water squeezing: utilize the water squeezing of through type wringing machine, look the crust leather moisture content and take the circumstances into consideration to squeeze 1 ~ 2 time; Require: crust leather moisture content 50% ~ 55%;
(4) shaving: shaving thickness 0.4 ~ 0.6mm (individual layer);
(5) weigh: accurately weigh, as the meter material foundation of following each operation;
(6) rinsing: 200 ~ 300 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 0.1 ~ 0.5 part of peregal, 0.1 ~ 0.5 part in formic acid rotates 60min, discharge opeing;
(7) neutralization: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 0.5 ~ 1.5 part of sodium bicarbonate, 0.5 ~ 1.5 part of neutralizing retanning agent rotates 30min, and adjusting the pH value is 4.5 ~ 5.0;
(8) retanning: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 1 ~ 3 part of sulfonation synthetic oil fatting agent JM, rotate 30min, add 1 ~ 3 part of DMT-II and cooperate 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 neutralization: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 0.5 ~ 1.5 part of sodium formiate, 1.0 ~ 1.5 parts of sodium thiosulfate rotate 40min, add 1 ~ 2 part of sodium bicarbonate, adjust pH5.5 ~ 6.0, rotate 120 ~ 240min, discharge opeing;
(10) washing: flowing water is washed 10min, discharge opeing;
(11) dyeing and fat-liquoring: 100 ~ 150 parts in water, temperature: 45 ~ 55 ℃, from drum gudgeon, add 2.0 ~ 2.5 parts of black matching stains, rotate 60min, add 2 ~ 6 parts of silicone based waterproof currying agents, 1 ~ 4 part of organic fluorine class water-resisting agent rotates 90min, add 0.5 ~ 1.5 part of formic acid, rotate 20min, add 1 ~ 5 part of Zirconium-aluminum-titanium and cooperate tanning agent (the DMT-I cooperates tanning agent) or 1 ~ 5 part of zirconium-aluminium to cooperate tanning agent (ZA joins and tanning agent), fix, adjust pH=4.0, rotate 40min;
(12) washing: 200 ~ 400 parts in water, temperature: room temperature, rotate 15min, discharge opeing;
(13) routinely technology carry out water squeezing stretching, extension, drying, moisture regain, toggling, fall soft;
In the tanning step:
Described Chrome-free multi-metal complex tanning agent, it is the metal composite tanning agent based on zirconates and aluminium salt; Preferably 12 ~ 15 parts of the consumptions of described Chrome-free multi-metal complex tanning agent.
Among the present invention:
Described ZA zirconium-aluminium cooperates tanning agent and DMT-I Zirconium-aluminum-titanium to cooperate tanning agent, and it is based on zirconates and aluminium salt that DMT-II Zirconium-aluminum-titanium cooperates tanning agent, by adding a kind of non-chromium cooperation tanning agent that multiple auxiliary agent is formed; Its technical indicator is as follows:
(1) outward appearance: white powder;
(2) solubleness: 30 ~ 50g/100g water (25 ℃);
(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 orders;
Used ZA cooperates tanning agent, DMT-I to cooperate tanning agent and DMT-II to cooperate tanning agent by Chengdu Bailejin Biological Scinece ﹠ Technology Co., Ltd.'s production and provides, and other chemical materialss are commercially available technical grade chemical.
Another technical scheme of the present invention is that a kind of two waterproof types that made by aforesaid method do not have the chrome tanning sheep skin, it is characterized in that its index that satisfies is as follows:
(1) according to the People's Republic of China (PRC) " clothes leather light industry standard " (QB/T3812.9-1999) " mensuration of leather shrinking temperature ", measures shrinkage temperature and can reach more than 90 ℃ not tempering stored for a long time;
(2) according to the QB/T 1275-1991 of the People's Republic of China (PRC) " mensuration of leather products-chromium sesquioxide ", measure this clothing leather product and do not contain chromium;
(3) People's Republic of China's light industry standard QB/T 1269-1991 " mensuration of leather products-elongation " measures tensile strength 〉=10N/mm
2, elongation at break 〉=60%;
(4) according to State Standard of the People's Republic of China GB/T 4689.21-2008 " leather-physics and mechanical testing-static absorptive test ", measure the static water regain of clothing leather and have only about 20%.
Embodiment:
Carry out concrete description below by the present invention of embodiment; only be used for the present invention is further specified; can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can make improvement and the adjustment of some non-intrinsically safes according to the content of foregoing invention to the present invention.
Embodiment 1:
(1) pre-treatment: the pelt after the softening pickling of the standard of getting, weigh, place in the suspension type wood rotary drum, hide increases weight to 150% ~ 200%, and the pelt meter in the rotary drum after the weightening finish heavily is 100 parts; Under the normal temperature, add 50 parts of acid solutions, add pretreating agent DMT-I and cooperate tanning agent or ZA to cooperate 1 part of tanning agent in rotary drum, rotate 20min, stop drum;
(2) tanning: open drum door, the DMT-II that adds 7 parts from drum door cooperates tanning agent (Zirconium-aluminum-titanium cooperation tanning agent DMT-II, Chengdu Bailejin Biological Scinece ﹠ Technology Co., Ltd., lot identification mark: 2012-05-08), rotate 120min continuously; Add 1 part of sodium formate solution (1:10 water dissolution) of dissolving in advance from drum gudgeon, rotate 10min, use 3.5 parts sodium bicarbonate (1:10 water dissolution) to carry alkali then, adjusting pH is 3.7 ~ 4.2; 100 parts of hot water that add 50 ~ 60 ℃ at last from drum gudgeon make the temperature of body lotion in the rotary drum rise to 40 ~ 45 ℃, rotate 120min continuously; Standing over night goes out drum after rotating 30min next day, leaves standstill 2 days;
(3) water squeezing: utilize the water squeezing of through type wringing machine, look the crust leather moisture content and take the circumstances into consideration to squeeze 1 ~ 2 time; Require: crust leather moisture content 50% ~ 55%;
(4) shaving: shaving thickness 0.4 ~ 0.6mm (individual layer);
(5) weigh: accurately weigh, as the meter material foundation of following each operation;
(6) rinsing: 200 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 0.2 part of peregal, 0.2 part in formic acid rotates 60min, discharge opeing;
(7) neutralization: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 1.0 parts of sodium bicarbonate, 1.0 parts of neutralizing retanning agents rotate 30min, and adjusting the pH value is 4.5 ~ 5.0;
(8) retanning: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 2 parts of sulfonation synthetic oil fatting agent JM, rotate 30min, add 2 parts of DMT-II and cooperate tanning agent (Zirconium-aluminum-titanium cooperation tanning agent DMT-II, Chengdu Bailejin Biological Scinece ﹠ Technology Co., Ltd., lot identification mark: 2012-05-08), rotate 90min; Add 1.0 parts of acrylic resin retanning agent ART-4(Guangdong and newly understand the chemical plant), rotate 30min, add 2 parts of maleic anhydride retanning agents (BSF(China) chemical industry company limited), rotate 40min; Add 1.0 parts of formic acid, adjust pH=4.0, rotate 20min;
(9) secondary neutralization: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 0.8 part of sodium formiate, 1.2 parts of sodium thiosulfate rotate 40min, add 1.5 parts of sodium bicarbonate, adjust pH5.5 ~ 6.0, rotate 120min, discharge opeing;
(10) washing: flowing water is washed 10min, discharge opeing;
(11) dyeing and fat-liquoring: 100 ~ 150 parts in water, temperature: 45 ~ 55 ℃, from drum gudgeon, add 2.0 parts of black matching stains, rotate 60min, add 2 parts of silicone based waterproof currying agent Densodrin CD(waterproof currying agent Densodrin CD, Germany BASF stock company, lot identification mark: 2012-04-21), 4 parts of organic fluorine class water-resisting agent Densodrin OF(waterproof currying agent Densodrin OF, German BASF stock company, lot identification mark: 2012-04-21), rotate 90min, add 0.8 part of formic acid, rotate 20min, add 3 parts of Zirconium-aluminum-titaniums and cooperate tanning agent (DMT-I cooperation tanning agent, Chengdu Bailejin Biological Scinece ﹠ Technology Co., Ltd., lot identification mark) fixes, adjust pH=4.0, rotate 40min;
(12) washing: 200 ~ 400 parts in water, temperature: room temperature, rotate 15min, discharge opeing;
(13) routinely technology carry out water squeezing stretching, extension, drying, moisture regain, toggling, fall soft.
Embodiment 2:
(1) pre-treatment: the pelt after the softening pickling of the standard of getting, weigh, place in the suspension type wood rotary drum, hide increases weight to 150% ~ 200%, and the pelt meter in the rotary drum after the weightening finish heavily is 100 parts; Under the normal temperature, add 50 parts of acid solutions, add pretreating agent DMT-I and cooperate tanning agent or ZA to cooperate 0.5 part of tanning agent in rotary drum, rotate 20min, stop drum;
(2) tanning: open drum door, the DMT-II that adds 10 parts from drum door cooperates tanning agent (Zirconium-aluminum-titanium cooperation tanning agent DMT-II, Chengdu Bailejin Biological Scinece ﹠ Technology Co., Ltd., lot identification mark: 2012-05-08), rotate 120min continuously; Add 1 part of sodium formate solution (1:10 water dissolution) of dissolving in advance from drum gudgeon, rotate 10min, use 2 parts sodium bicarbonate (1:10 water dissolution) to carry alkali then, adjusting pH is 3.7 ~ 4.2; 100 parts of hot water that add 50 ~ 60 ℃ at last from drum gudgeon make the temperature of body lotion in the rotary drum rise to 40 ~ 45 ℃, rotate 120min continuously; Standing over night goes out drum after rotating 30min next day, leaves standstill 2 days;
(3) water squeezing: utilize the water squeezing of through type wringing machine, look the crust leather moisture content and take the circumstances into consideration to squeeze 1 ~ 2 time; Require: crust leather moisture content 50% ~ 55%;
(4) shaving: shaving thickness 0.4 ~ 0.6mm (individual layer);
(5) weigh: accurately weigh, as the meter material foundation of following each operation;
(6) rinsing: 200 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 0.2 part of peregal, 0.1 part in formic acid rotates 60min, discharge opeing;
(7) neutralization: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 1.0 parts of sodium bicarbonate, 1.0 parts of neutralizing retanning agents rotate 30min, and adjusting the pH value is 4.5 ~ 5.0;
(8) retanning: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 1 part of sulfonation synthetic oil fatting agent JM, rotate 30min, add 1 part of DMT-II and cooperate tanning agent (Zirconium-aluminum-titanium cooperation tanning agent DMT-II, Chengdu Bailejin Biological Scinece ﹠ Technology Co., Ltd., lot identification mark: 2012-05-08), rotate 90min; Add 0.5 part of acrylic resin retanning agent ART-4(Guangdong and newly understand the chemical plant), rotate 30min, add 1 part of maleic anhydride retanning agent (BSF(China) chemical industry company limited), rotate 40min; Add 1 part of formic acid, adjust pH=4.0, rotate 20min;
(9) secondary neutralization: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 0.5 part of sodium formiate, 1.0 parts of sodium thiosulfate rotate 40min, add 2.0 parts of sodium bicarbonate, adjust pH5.5 ~ 6.0, rotate 120min, discharge opeing;
(10) washing: flowing water is washed 10min, discharge opeing;
(11) dyeing and fat-liquoring: 100 ~ 150 parts in water, temperature: 45 ~ 55 ℃, from drum gudgeon, add 2.0 parts of black matching stains, rotate 60min, add 4 parts of silicone based waterproof currying agent Densodrin CD(waterproof currying agent Densodrin CD, Germany BASF stock company, lot identification mark: 2012-04-21), 2 parts of organic fluorine class water-resisting agent Densodrin OF(waterproof currying agent Densodrin OF, Germany BASF stock company, lot identification mark: 2012-04-21), rotate 90min, add 0.8 part of formic acid, rotate 20min, cooperate tanning agent (ZA joins and tanning agent, Chengdu Bailejin Biological Scinece ﹠ Technology Co., Ltd.) to fix with 3 parts of zirconiums-aluminium, adjust pH=4.0, rotate 40min;
(12) washing: 200 ~ 400 parts in water, temperature: room temperature, rotate 15min, discharge opeing;
(13) routinely technology carry out water squeezing stretching, extension, drying, moisture regain, toggling, fall soft.
Embodiment 3:
(1) pre-treatment: the pelt after the softening pickling of the standard of getting is weighed, and places in the suspension type wood rotary drum, and hide increases weight to 150% ~ 200%, and the pelt meter in the rotary drum after the weightening finish heavily is 100 parts; Under the normal temperature, add 50 parts of acid solutions, add pretreating agent DMT-I and cooperate tanning agent or ZA to cooperate 2 parts of tanning agents in rotary drum, rotate 20min, stop drum;
(2) tanning: open drum door, the DMT-II that adds 15 parts from drum door cooperates tanning agent (Zirconium-aluminum-titanium cooperation tanning agent DMT-II, Chengdu Bailejin Biological Scinece ﹠ Technology Co., Ltd., lot identification mark: 2012-05-08), rotate 120min continuously; Add 1 part of sodium formate solution (1:10 water dissolution) of dissolving in advance from drum gudgeon, rotate 10min, use 4 parts sodium bicarbonate (1:10 water dissolution) to carry alkali then, adjusting pH is 3.7 ~ 4.2; 100 parts of hot water that add 50 ~ 60 ℃ at last from drum gudgeon make the temperature of body lotion in the rotary drum rise to 40 ~ 45 ℃, rotate 120min continuously; Standing over night goes out drum after rotating 30min next day, leaves standstill 2 days;
(3) water squeezing: utilize the water squeezing of through type wringing machine, look the crust leather moisture content and take the circumstances into consideration to squeeze 1 ~ 2 time; Require: crust leather moisture content 50% ~ 55%;
(4) shaving: shaving thickness 0.4 ~ 0.6mm (individual layer);
(5) weigh: accurately weigh, as the meter material foundation of following each operation;
(6) rinsing: 200 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 0.2 part of peregal, 0.2 part in formic acid rotates 60min, discharge opeing;
(7) neutralization: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 1.0 parts of sodium bicarbonate, 1.0 parts of neutralizing retanning agents rotate 30min, and adjusting the pH value is 4.5 ~ 5.0;
(8) retanning: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 3 parts of sulfonation synthetic oil fatting agent JM, rotate 30min, add 3 parts of DMT-II and cooperate tanning agent (Zirconium-aluminum-titanium cooperation tanning agent DMT-II, Chengdu Bailejin Biological Scinece ﹠ Technology Co., Ltd., lot identification mark: 2012-05-08), rotate 90min; Add 1.0 parts of acrylic resin retanning agent ART-4(Guangdong and newly understand the chemical plant), rotate 30min, add 1 part of maleic anhydride retanning agent (BSF(China) chemical industry company limited), rotate 40min; Add 0.8 part of formic acid, adjust pH=4.0, rotate 20min;
(9) secondary neutralization: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 1.5 parts of sodium formiates, 1.0 parts of sodium thiosulfate rotate 40min, add 1 part of sodium bicarbonate, adjust pH5.5 ~ 6.0, rotate 120min, discharge opeing;
(10) washing: flowing water is washed 10min, discharge opeing;
(11) dyeing and fat-liquoring: 100 ~ 150 parts in water, temperature: 45 ~ 55 ℃, from drum gudgeon, add 2.0 parts of black matching stains, rotate 60min, add 6 parts of silicone based waterproof currying agent Densodrin CD(waterproof currying agent Densodrin CD, Germany BASF stock company, lot identification mark: 2012-04-21), 1 part of organic fluorine class water-resisting agent Densodrin OF(waterproof currying agent Densodrin OF, German BASF stock company, lot identification mark: 2012-04-21), rotate 90min, add 0.8 part of formic acid, rotate 20min, add 5 parts of Zirconium-aluminum-titaniums and cooperate tanning agent (DMT-I cooperation tanning agent, Chengdu Bailejin Biological Scinece ﹠ Technology Co., Ltd., lot identification mark) fixes, adjust pH=4.0, rotate 40min;
(12) washing: 200 ~ 400 parts in water, temperature: room temperature, rotate 15min, discharge opeing;
(13) routinely technology carry out water squeezing stretching, extension, drying, moisture regain, toggling, fall soft.
Claims (7)
1. the Zirconium-aluminum-titanium waterproof garment leather and preparation method thereof of tanning is characterized in that:
(1) shrinkage temperature 〉=90 ℃;
(2) Cr
3+: can't check;
(3) Cr
6+: can't check;
(4) tensile strength 〉=10N/mm
2, elongation at break 〉=60%, tear strength 〉=30/N/mm, height 〉=9mm bursts apart;
(5) the static water regain of leather has only about 20%;
(6) storge quality: store more than 2 years, organoleptic properties and physicochemical property remain unchanged;
(7) leather-making mud can directly burn, and does not have potential sexavalent chrome danger.
2. the Zirconium-aluminum-titanium waterproof garment leather and preparation method thereof of tanning is characterized in that, may further comprise the steps, wherein the equal meter by weight of material therefor:
(1) pre-treatment: the pelt after the softening pickling of the standard of getting, weigh, place in the suspension type wood rotary drum, hide increases weight to 150% ~ 200%, and the pelt meter in the rotary drum after the weightening finish heavily is 100 parts; Under the normal temperature, add 50 ~ 150 parts of acid solutions, add pretreating agent DMT-I and cooperate tanning agent or ZA to cooperate 0.5 ~ 2.5 part of tanning agent in rotary drum, rotate 10 ~ 50min, stop drum;
(2) tanning: open drum door, the DMT-II that adds 7 ~ 20 parts from drum door cooperates tanning agent, rotates 120 ~ 240min continuously; Add 1 ~ 3 part of sodium formate solution (1:10 water dissolution) of dissolving in advance from drum gudgeon, rotate 10 ~ 50min, use 2 ~ 5 parts sodium bicarbonate (1:10 water dissolution) to carry alkali then, adjusting pH is 3.7 ~ 4.2; 100 ~ 200 parts of hot water that add 50 ~ 60 ℃ at last from drum gudgeon make the temperature of body lotion in the rotary drum rise to 40 ~ 45 ℃, rotate 120 ~ 240min continuously; Standing over night goes out drum after rotating 30min next day, leaves standstill 2 days;
(3) water squeezing: utilize the water squeezing of through type wringing machine, look the crust leather moisture content and take the circumstances into consideration to squeeze 1 ~ 2 time; Require: crust leather moisture content 50% ~ 55%;
(4) shaving: shaving thickness 0.4 ~ 0.6mm (individual layer);
(5) weigh: accurately weigh, as the meter material foundation of following each operation;
(6) rinsing: 200 ~ 300 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 0.1 ~ 0.5 part of peregal, 0.1 ~ 0.5 part in formic acid rotates 60min, discharge opeing;
(7) neutralization: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 0.5 ~ 1.5 part of sodium bicarbonate, 0.5 ~ 1.5 part of neutralizing retanning agent rotates 30min, and adjusting the pH value is 4.5 ~ 5.0;
(8) retanning: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 1 ~ 3 part of sulfonation synthetic oil fatting agent JM, rotate 30min, add 1 ~ 3 part of DMT-II and cooperate 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 neutralization: 100 ~ 150 parts in water, temperature: 32 ~ 35 ℃, from drum gudgeon, add 0.5 ~ 1.5 part of sodium formiate, 1.0 ~ 1.5 parts of sodium thiosulfate rotate 40min, add 1 ~ 2 part of sodium bicarbonate, adjust pH5.5 ~ 6.0, rotate 120 ~ 240min, discharge opeing;
(10) washing: flowing water is washed 10min, discharge opeing;
(11) dyeing and fat-liquoring: 100 ~ 150 parts in water, temperature: 45 ~ 55 ℃, from drum gudgeon, add 2.0 ~ 2.5 parts of black matching stains, rotate 60min, add 2 ~ 6 parts of silicone based waterproof currying agents, 1 ~ 4 part of organic fluorine class water-resisting agent rotates 90min, add 0.5 ~ 1.5 part of formic acid, rotate 20min, add 1 ~ 5 part of Zirconium-aluminum-titanium and cooperate tanning agent (the DMT-I cooperates tanning agent) or 1 ~ 5 part of zirconium-aluminium to cooperate tanning agent (ZA cooperates tanning agent), fix, adjust pH=4.0, rotate 40min;
(12) washing: 200 ~ 400 parts in water, temperature: room temperature, rotate 15min, discharge opeing;
(13) routinely technology carry out water squeezing stretching, extension, drying, moisture regain, toggling, fall soft.
3. the stdn described in the claim 2 acid skin technology, its technology is:
Raw material is liming ox-hide, pigskin, the sheepskin that cuts open behind the layer, and thickness 2.0 ~ 3.0mm, graywall poidometer heavily are 100 parts;
(1) washing: water 100%, temperature: 37 ℃, rotate 15min, discharge opeing;
(2) deliming: water reaches Willie card DLA for 100%, 2 part does not have the ammonia deliming agent, and 1 part of lactic acid rotates 30min, rotating speed 16rpm;
(3) softening: as to add 0.2 part prozyme F, rotate 60min, rotating speed 16 rpm, discharge opeing;
(4) washing: water 100%, normal temperature rotates 15min, discharge opeing;
(5) pickling: water 50%, temperature: normal temperature; Open drum door, from drum gudgeon, add 7 parts of industrial table salts, rotate 10min, from drum gudgeon, add then and dissolve 0.8 part in formic acid (dilution of 1:20 water dissolution) completely in advance, rotate 30min, from drum gudgeon, add 1.2 parts in sulfuric acid (dilution of 1:20 water dissolution), make pH=2.6 ~ 2.8, rotate 120min.
4. the described Zirconium-aluminum-titanium of claim 2 method of waterproof garment leather of tanning is characterized in that described pretreating agent DMT-I cooperates tanning agent or ZA to cooperate tanning agent, and the consumption of Zirconium-aluminum-titanium title complex tanning agent is 7 ~ 20 parts.
5. the DMT-I described in the claim 2,3 cooperates tanning agent, DMT-II to cooperate tanning agent, ZA cooperation tanning agent, prozyme F to be Chengdu Bailejin Biological Scinece ﹠ Technology Co., Ltd.'s production and (but to defend China, Chen Zhe, but time, etc. the many metals of zirconium-aluminium cooperate the preparation method of owse. number of patent application: 201110114107.5; But defend China, but time, vast stretch of wooded country, etc. Zirconium-aluminum-titanium multi-metal complex pulvis and preparation method thereof. the patent No.: ZL 200710048440.4; But defend China, Ceng Rui, Liao Longli is etc. prozyme collagen treatment agent. the patent No.: ZL 03117914.2) reaching Willie card DLA, not have the ammonia deliming agent be that Sichuan Dowell Technology Co., Ltd. produces; Other material is commercially available technical grade chemical.
6. the described suspension type wood rotary drum of claim 2 is produced for Yancheng City generation mark leather rotary drum machinery company limited.
7. tan waterproof garment leather of the described Zirconium-aluminum-titanium of claim 2, it is characterized in that: the static water regain of finished leather is lower than 20%.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104988250A (en) * | 2015-06-23 | 2015-10-21 | 兴业皮革科技股份有限公司 | Cattle instep leather less chrome tanning method based on zirconium-aluminum-titanium matched tanning agent |
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| CN115838841A (en) * | 2022-11-28 | 2023-03-24 | 中国皮革和制鞋工业研究院（晋江）有限公司 | Method for preparing waterproof leather by using zeolite tanning agent and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016572A (en) * | 2007-02-09 | 2007-08-15 | 四川大学 | Zirconium-aluminum-titanium multi-metal complex powder and preparing method thereof |
| CN101993962A (en) * | 2009-08-27 | 2011-03-30 | 际华三五一五皮革皮鞋有限公司 | Method for manufacturing waterproof soft-surface leather |
| CN102206717A (en) * | 2011-05-04 | 2011-10-05 | 四川大学 | Method for preparing zirconium-aluminum multi-metal tanning liquor |
| CN102787181A (en) * | 2012-08-01 | 2012-11-21 | 四川大学 | Zirconium-aluminum-titanium complex tanning agent based less-chrome tanning method |
-
2013
- 2013-04-22 CN CN201310139057.5A patent/CN103194548B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016572A (en) * | 2007-02-09 | 2007-08-15 | 四川大学 | Zirconium-aluminum-titanium multi-metal complex powder and preparing method thereof |
| CN101993962A (en) * | 2009-08-27 | 2011-03-30 | 际华三五一五皮革皮鞋有限公司 | Method for manufacturing waterproof soft-surface leather |
| CN102206717A (en) * | 2011-05-04 | 2011-10-05 | 四川大学 | Method for preparing zirconium-aluminum multi-metal tanning liquor |
| CN102787181A (en) * | 2012-08-01 | 2012-11-21 | 四川大学 | Zirconium-aluminum-titanium complex tanning agent based less-chrome tanning method |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104988250A (en) * | 2015-06-23 | 2015-10-21 | 兴业皮革科技股份有限公司 | Cattle instep leather less chrome tanning method based on zirconium-aluminum-titanium matched 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 |
| CN105671221A (en) * | 2015-07-08 | 2016-06-15 | 四川大学 | Cattle hide upper leather with double waterproof layers and preparation method thereof |
| CN105155307A (en) * | 2015-08-27 | 2015-12-16 | 兴业皮革科技股份有限公司 | Wet-state dyeing finishing and fixation method for leathers based on zirconium-aluminum-titanium complex |
| CN105349710A (en) * | 2015-12-17 | 2016-02-24 | 湖南科技职业学院 | Chromium-free combination tannage method for cattle hides |
| 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 |
| CN105994000A (en) * | 2016-05-24 | 2016-10-12 | 辽宁富新新材料有限公司 | Dog-chewing gum and preparation method thereof |
| CN106282439A (en) * | 2016-09-22 | 2017-01-04 | 湖州东方皮革有限公司 | A kind of water-fastness, environment-friendly type clothing leather processing technique |
| CN115838841A (en) * | 2022-11-28 | 2023-03-24 | 中国皮革和制鞋工业研究院（晋江）有限公司 | Method for preparing waterproof leather by using zeolite tanning agent and application thereof |
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