CN104988250A - Cattle instep leather less chrome tanning method based on zirconium-aluminum-titanium matched tanning agent - Google Patents
Cattle instep leather less chrome tanning method based on zirconium-aluminum-titanium matched tanning agent Download PDFInfo
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- CN104988250A CN104988250A CN201510347426.9A CN201510347426A CN104988250A CN 104988250 A CN104988250 A CN 104988250A CN 201510347426 A CN201510347426 A CN 201510347426A CN 104988250 A CN104988250 A CN 104988250A
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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
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
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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
- C14C3/04—Mineral tanning
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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
- C14C3/04—Mineral tanning
- C14C3/06—Mineral tanning using chromium compounds
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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
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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
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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
- C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
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- 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
- C14C3/28—Multi-step processes
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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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
Abstract
The invention relates to the technical field of tanning chemistry and engineering and provides a cattle instep leather less chrome tanning method based on a zirconium-aluminum-titanium matched tanning agent. In a tanning workshop section, the combined use of the zirconium-aluminum-titanium matched tanning agent and a chrome tanning agent is adopted, wherein the use amount of the chrome tanning agent is only 30-40% of the use amount of that in a conventional process, the chrome content in tanning waste liquor can be reduced by 80%, the shrinkage temperature of crust leather exceeds 95 DEG C, and various physical and mechanical properties meet industrial standards. The crust leather produced by the method also has the following advantages that the color is light, and the production of light-color leather is facilitated; the yield of leather is high, and the economic benefits of enterprises are increased; the grain side is flat and fine; the crust leather is suitable for producing top grade leather such as full grain leather, nappa leather and natural-fall instep leather and the like. According to the cattle instep leather less chrome tanning method based on the zirconium-aluminum-titanium matched tanning agent, not only can the use amount of the chrome in the tanning production be reduced, the chrome emission reduced and harm of the chrome to environment reduced, but also the overall performance of existing cattle instep leather can be improved, and the production technology achieves high benefits, cleanness and environmental protection.
Description
Technical field
The present invention relates to tanning chemistry and field of engineering technology, particularly a kind of cattle hide upper leather less chrome tannage method coordinating tanning agent based on Zirconium-aluminum-titanium.
Background technology
Now, leather industry pollution of chromium problem enjoys social concerns, " process hides and the fur manufacturing industrial water pollution thing emission standard " regulation put into effect for 2014, in the comprehensive wastewater of existing leather-making enterprises discharge, total chrome content must not more than 1.5mg/L, and content of 6-valence Cr ions need lower than 0.2mg/L.The increasingly stringent of environmental protection policy regulation makes the use of chromic tanning be restricted, and this also constrains the development of leather industry.For this reason, reduce the pollution of chromium, develop the less chrome tannage technology cleaned, be the great demand of country, realizing the inexorable trend of tanning industry Sustainable development, is also the target that leather industry is dreamed of.
At present comparatively ripe less chrome tannage technology is following three kinds: 1) vegetable tanning agent-chromium Combined tanning, by vegetable tanning agent is carried out modified with chrome tanning agent in conjunction with tanning, utilize the synergy between plant polyphenol and chromium to improve tanning agent tanning effect; 2) organic tanning agent-chromium Combined tanning, by utilizing acrylic resin, aldehydes tanning agent carries out pretan, improve collegen filament tan before state, in skin, introduce more functional group, play the object promoting chrome tanning agent infiltration, improve combination rate; 3) chromium-non-chromium melts combine tannage, utilizes the synergy between many metals, plays the independent tanning advantage of each metal, improves the aesthetic quality of finished leather.
By introducing few chrome tanning technology in cow leather upper leather being produced, not only alleviating tanning production pollution of chromium problem, meeting national requirements for environmental protection.Also can give finished leather more characteristic adding of novel material simultaneously, the integrated quality of upper leather further be promoted, meets the consumers demand that people are growing, upper leather Future Development is significant.
Summary of the invention
Therefore, for above-mentioned problem, the present invention proposes a kind of cattle hide upper leather less chrome tannage method coordinating tanning agent based on Zirconium-aluminum-titanium, the described cattle hide upper leather less chrome tannage method based on Zirconium-aluminum-titanium cooperation tanning agent not only can reduce the consumption of chromium in tanning production, reduce chromium discharge, alleviate the harm of chromium to environment, simultaneously, can promote the over-all properties of existing cattle hide upper leather, be a kind of high benefit clean environment firendly production technology.
For realizing above-mentioned technical problem, the solution that the present invention takes is: a kind of cattle hide upper leather less chrome tannage method coordinating tanning agent based on Zirconium-aluminum-titanium, comprises the steps:
Step 1, get the grey alkali skin after cuing open layer and weigh, as deliming, softening, pickling, tanning process meter material foundation;
Step 2, cut open conveniently technique deliming, softening, the pickling of the grey alkali skin after layer, pickling terminal pH is 2.5-2.7;
Step 3, tanning: in rotary drum under bath temperature 25 DEG C of conditions, add grease material or the aldehydes material processing pickled pelt of ash charge alkali tare weight amount 1%-3%, rotate 30 minutes; Then with the chrome tanning agent adding ash charge alkali tare weight amount 1%-3% in bath, 1.5-2.5 hour is rotated; Coordinate tanning agent with the Zirconium-aluminum-titanium adding ash charge alkali tare weight amount 10%-20% in bath again, rotate 2-3 hour; Stop drum hold over night; After rotating 30 minutes next day, add the sodium formiate of ash charge alkali tare weight amount 1%, rotate 20 minutes; Carry alkali with the water-soluble saleratus solution of 1:20 again, make terminal pH be 4.0-4.2; Add the hot water of 50-60 DEG C of grey alkali tare weight amount 100%, make the liquor ratio of body lotion reach 2.0, make bath temperature rise to 40 DEG C, continuation effect 3-4 hour, goes out drum, takes horse and leaves standstill 48 hours;
Step 4, leave standstill after crust leather water squeezing, shaving, weigh, as follow-up hygrometric state dyeing and finishing workshop section meter material foundation;
Step 5, hygrometric state dyeing and finishing: the synthetic tanning agent adding shaving leather weight 8%-18% in hygrometric state dyeing and finishing workshop section, the vegetable tanning agent of shaving leather weight 3%-7%, the fatting agent process crust leather of shaving leather weight 12%-16%;
After step 6, hygrometric state dyeing and finishing terminate, conveniently technique carries out dry state ornamenting.
Further, the grease material in step 3 is at least one in cationic fatliquor, anionic fatting agent, non-ionic type fatting agent.
Further, the aldehydes material in step 3 is at least one in formaldehyde, glutaraldehyde, aldehydic acid.
Further, the chrome tanning agent in step 3 is commercial goods, and its chromic oxide content is 23% ± 2%; Described Zirconium-aluminum-titanium coordinates tanning agent to be the product that Jin Kun Chemical Co., Ltd. of Mianzhu City produces, and its total oxide content is 9% ± 2%.
Further, the synthetic tanning agent in step 5 is at least one in acrylic acid or the like tanning agent, aminoresin class tanning agent, phenol sulphonic acids tanning agent, aldehydes tanning agent.
Further, the vegetable tanning agent in step 5 is at least one in wattle extract tanning agent, myrica extract tanning agent, nutgall tannin extract tanning agent, valonex tanning agent, quebracho extract.
Further, the fatting agent in step 5 is at least one in lanolin fatting agent, fish oil fatliquoring agent, Yelkin TTS fatting agent, vegetables oil fatting agent, mineral oil fatting agent, synthetic fat liquor.
By adopting preceding solution, the invention has the beneficial effects as follows: the cattle hide upper leather less chrome tannage method based on Zirconium-aluminum-titanium cooperation tanning agent of design as mentioned above has following advantage compared to prior art: 1, in tanning, chrome tanning agent consumption is only the 30%-40% of common process consumption, waste tanning liquor chromium content reduces 80%, alleviates tanning production pollution of chromium; 2, gained crust leather color and luster is light, grain is flat thin, can be used for producing full grain, nappa leather, naturally falling the high-grade productions of removing from office such as upper leather; 3, finished leather yield of leather is high, can increase Business Economic Benefit.
Embodiment
Describe embodiments of the present invention in detail below with reference to specific embodiment, to the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure reaching technique effect can fully understand and implement according to this.If do not specialize, the conventional means that the technique means adopted in embodiment is well known to those skilled in the art, the reagent adopted and product be also can business obtain.The various process do not described in detail and method are ordinary methods as known in the art, source, the trade(brand)name of agents useful for same and be necessary to list its moiety person, all indicate when occurring first.
Embodiment 1
(1) get the grey alkali skin after cuing open layer to weigh, as deliming, softening, pickling, tanning process meter material foundation;
(2) cut open conveniently technique deliming, softening, the pickling of the grey alkali skin after layer, pickling terminal pH is 2.5-2.7;
(3) tanning: in rotary drum under bath temperature 25 DEG C of conditions, adds the glutaraldehyde process pickled pelt of ash charge alkali tare weight amount 3%, rotates 30 minutes; Then with the chrome tanning agent (commercial goods, its chromic oxide content is 23% ± 2%) adding ash charge alkali tare weight amount 1% in bath, rotate 1.5 hours; Coordinate tanning agent (Jin Kun Chemical Co., Ltd. of Mianzhu City produces, and its total oxide content is 9% ± 2%) with the Zirconium-aluminum-titanium adding ash charge alkali tare weight amount 20% in bath again, rotate 3 hours; Stop drum hold over night; After rotating 30 minutes next day, add the sodium formiate of ash charge alkali tare weight amount 1%, rotate 20 minutes; Carry alkali with the water-soluble saleratus solution of 1:20 again, make terminal pH be 4.2; Add the hot water of 50-60 DEG C of grey alkali tare weight amount 100%, make the liquor ratio of body lotion reach 2.0, make bath temperature rise to 40 DEG C, continuation acts on 4 hours, goes out drum, takes horse and leaves standstill 48 hours;
(4) leave standstill rear crust leather water squeezing, shaving, weigh, as follow-up hygrometric state dyeing and finishing workshop section meter material foundation;
(5) hygrometric state dyeing and finishing: aminoresin class tanning agent (the Lang Sheng Chemical Co., Ltd. adding shaving leather weight 3% in hygrometric state dyeing and finishing workshop section, R7), acrylic acid or the like tanning agent (the BASF limited liability company of shaving leather weight 4%, RE), phenol sulphonic acids tanning agent (the BASF limited liability company of shaving leather weight 1%, TM), the wattle extract tanning agent (Mimosa company) of shaving leather weight 3%, fish oil fatliquoring agent (the German Sima Chemical Co., Ltd. of shaving leather weight 4%, AM90), synthetic fat liquor (the German Sima Chemical Co., Ltd. of shaving leather weight 5%, SP), Yelkin TTS fatting agent (the German Sima Chemical Co., Ltd. of shaving leather weight 4%, BA), lanolin fatting agent (the German Sima Chemical Co., Ltd. of shaving leather weight 3%, 100), process crust leather,
(6), after hygrometric state dyeing and finishing terminates, conveniently technique carries out dry state ornamenting.
Embodiment 2
(1) get the grey alkali skin after cuing open layer to weigh, as deliming, softening, pickling, tanning process meter material foundation;
(2) cut open conveniently technique deliming, softening, the pickling of the grey alkali skin after layer, pickling terminal pH is 2.5-2.7;
(3) tanning: in rotary drum under bath temperature 25 DEG C of conditions, adds the glutaraldehyde process pickled pelt of ash charge alkali tare weight amount 2%, rotates 30 minutes; Then with the chrome tanning agent adding ash charge alkali tare weight amount 2% in bath, rotate 2 hours; Coordinate tanning agent with the Zirconium-aluminum-titanium adding ash charge alkali tare weight amount 15% in bath again, rotate 2.5 hours; Stop drum hold over night; After rotating 30 minutes next day, add the sodium formiate of ash charge alkali tare weight amount 1%, rotate 20 minutes; Carry alkali with the water-soluble saleratus solution of 1:20 again, make terminal pH be 4.1; Add the hot water of 50-60 DEG C of grey alkali tare weight amount 100%, make the liquor ratio of body lotion reach 2.0, make bath temperature rise to 40 DEG C, continuation acts on 3.5 hours, goes out drum, takes horse and leaves standstill 48 hours;
(4) leave standstill rear crust leather water squeezing, shaving, weigh, as follow-up hygrometric state dyeing and finishing workshop section meter material foundation;
(5) hygrometric state dyeing and finishing: aminoresin class tanning agent (the Lang Sheng Chemical Co., Ltd. adding shaving leather weight 4% in hygrometric state dyeing and finishing workshop section, R7), acrylic acid or the like tanning agent (the BASF limited liability company of shaving leather weight 5%, RE), phenol sulphonic acids tanning agent (the BASF limited liability company of shaving leather weight 2%, TM), aldehydes tanning agent (the BASF limited liability company of shaving leather weight 2%, GT-50), the wattle extract tanning agent (Mimosa company) of shaving leather weight 5%, fish oil fatliquoring agent (the German Sima Chemical Co., Ltd. of shaving leather weight 4%, AM90), synthetic fat liquor (the German Sima Chemical Co., Ltd. of shaving leather weight 4%, SP), Yelkin TTS fatting agent (the German Sima Chemical Co., Ltd. of shaving leather weight 3%, BA), lanolin fatting agent (the German Sima Chemical Co., Ltd. of shaving leather weight 3%, 100), process crust leather,
(6), after hygrometric state dyeing and finishing terminates, conveniently technique carries out dry state ornamenting.
Embodiment 3
(1) get the grey alkali skin after cuing open layer to weigh, as deliming, softening, pickling, tanning process meter material foundation;
(2) cut open conveniently technique deliming, softening, the pickling of the grey alkali skin after layer, pickling terminal pH is 2.5-2.7;
(3) tanning: in rotary drum under bath temperature 25 DEG C of conditions, adds the cationic fat liquor process pickled pelt of ash charge alkali tare weight amount 1%, rotates 30 minutes; Then with the chrome tanning agent adding ash charge alkali tare weight amount 3% in bath, rotate 2.5 hours; Coordinate tanning agent with the Zirconium-aluminum-titanium adding ash charge alkali tare weight amount 10% in bath again, rotate 2 hours; Stop drum hold over night; After rotating 30 minutes next day, add the sodium formiate of ash charge alkali tare weight amount 1%, rotate 20 minutes; Carry alkali with the water-soluble saleratus solution of 1:20 again, make terminal pH be 4.0; Add the hot water of 50-60 DEG C of grey alkali tare weight amount 100%, make the liquor ratio of body lotion reach 2.0, make bath temperature rise to 40 DEG C, continuation acts on 3 hours, goes out drum, takes horse and leaves standstill 48 hours;
(4) leave standstill rear crust leather water squeezing, shaving, weigh, as follow-up hygrometric state dyeing and finishing workshop section meter material foundation;
(5) hygrometric state dyeing and finishing: add aminoresin class tanning agent (the Lang Sheng Chemical Co., Ltd. of 5% in hygrometric state dyeing and finishing workshop section, R7), acrylic acid or the like tanning agent (the BASF limited liability company of shaving leather weight 6%, RE), phenol sulphonic acids tanning agent (the BASF limited liability company of shaving leather weight 4%, TM), aldehydes tanning agent (the BASF limited liability company of shaving leather weight 3%, GT-50), the wattle extract tanning agent (Mimosa company) of shaving leather weight 7%, fish oil fatliquoring agent (the German Sima Chemical Co., Ltd. of shaving leather weight 3%, AM90), synthetic fat liquor (the German Sima Chemical Co., Ltd. of shaving leather weight 4%, SP), Yelkin TTS fatting agent (the German Sima Chemical Co., Ltd. of shaving leather weight 3%, BA), lanolin fatting agent (the German Sima Chemical Co., Ltd. of shaving leather weight 2%, 100),
(6), after hygrometric state dyeing and finishing terminates, conveniently technique carries out dry state ornamenting.
Above, be only the embodiment utilizing this origination techniques content, the modification that any those skilled in the art use this creation to do, change, all belong to the scope of the claims that this creation is advocated, and be not limited to those disclosed embodiments.
Claims (7)
1. coordinate a cattle hide upper leather less chrome tannage method for tanning agent based on Zirconium-aluminum-titanium, it is characterized in that, comprise the steps:
Step 1, get the grey alkali skin after cuing open layer and weigh, as deliming, softening, pickling, tanning process meter material foundation;
Step 2, cut open conveniently technique deliming, softening, the pickling of the grey alkali skin after layer, pickling terminal pH is 2.5-2.7;
Step 3, tanning: in rotary drum under bath temperature 25 DEG C of conditions, add grease material or the aldehydes material processing pickled pelt of ash charge alkali tare weight amount 1%-3%, rotate 30 minutes; Then with the chrome tanning agent adding ash charge alkali tare weight amount 1%-3% in bath, 1.5-2.5 hour is rotated; Coordinate tanning agent with the Zirconium-aluminum-titanium adding ash charge alkali tare weight amount 10%-20% in bath again, rotate 2-3 hour; Stop drum hold over night; After rotating 30 minutes next day, add the sodium formiate of ash charge alkali tare weight amount 1%, rotate 20 minutes; Carry alkali with the water-soluble saleratus solution of 1:20 again, make terminal pH be 4.0-4.2; Add the hot water of 50-60 DEG C of grey alkali tare weight amount 100%, make the liquor ratio of body lotion reach 2.0, make bath temperature rise to 40 DEG C, continuation effect 3-4 hour, goes out drum, takes horse and leaves standstill 48 hours;
Step 4, leave standstill after crust leather water squeezing, shaving, weigh, as follow-up hygrometric state dyeing and finishing workshop section meter material foundation;
Step 5, hygrometric state dyeing and finishing: the synthetic tanning agent adding shaving leather weight 8%-18% in hygrometric state dyeing and finishing workshop section, the vegetable tanning agent of shaving leather weight 3%-7%, the fatting agent process crust leather of shaving leather weight 12%-16%;
After step 6, hygrometric state dyeing and finishing terminate, conveniently technique carries out dry state ornamenting.
2. the cattle hide upper leather less chrome tannage method coordinating tanning agent based on Zirconium-aluminum-titanium according to claim 1, is characterized in that: the grease material in step 3 is at least one in cationic fatliquor, anionic fatting agent, non-ionic type fatting agent.
3. the cattle hide upper leather less chrome tannage method coordinating tanning agent based on Zirconium-aluminum-titanium according to claim 1, is characterized in that: the aldehydes material in step 3 is at least one in formaldehyde, glutaraldehyde, aldehydic acid.
4. the cattle hide upper leather less chrome tannage method coordinating tanning agent based on Zirconium-aluminum-titanium according to claim 1, it is characterized in that: the chrome tanning agent in step 3 is commercial goods, its chromic oxide content is 23% ± 2%; Described Zirconium-aluminum-titanium coordinates tanning agent to be the product that Jin Kun Chemical Co., Ltd. of Mianzhu City produces, and its total oxide content is 9% ± 2%.
5. the cattle hide upper leather less chrome tannage method coordinating tanning agent based on Zirconium-aluminum-titanium according to claim 1, is characterized in that: the synthetic tanning agent in step 5 is at least one in acrylic acid or the like tanning agent, aminoresin class tanning agent, phenol sulphonic acids tanning agent, aldehydes tanning agent.
6. the cattle hide upper leather less chrome tannage method coordinating tanning agent based on Zirconium-aluminum-titanium according to claim 1, is characterized in that: the vegetable tanning agent in step 5 is at least one in wattle extract tanning agent, myrica extract tanning agent, nutgall tannin extract tanning agent, valonex tanning agent, quebracho extract.
7. the cattle hide upper leather less chrome tannage method coordinating tanning agent based on Zirconium-aluminum-titanium according to claim 1, is characterized in that: the fatting agent in step 5 is at least one in lanolin fatting agent, fish oil fatliquoring agent, Yelkin TTS fatting agent, vegetables oil fatting agent, mineral oil fatting agent, synthetic fat liquor.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105907899A (en) * | 2016-05-18 | 2016-08-31 | 兴业皮革科技股份有限公司 | Leather black-dyeing method |
| CN107881269A (en) * | 2017-11-30 | 2018-04-06 | 兴业皮革科技股份有限公司 | A kind of production method of water proof fire retardant upper leather |
| CN113201605A (en) * | 2021-04-15 | 2021-08-03 | 兴业皮革科技股份有限公司 | Tanning process for multi-component chrome-free combined tanned white wet leather of cattle and application thereof |
| CN113278744A (en) * | 2021-06-05 | 2021-08-20 | 百草边大生物科技(青岛)有限公司 | Preparation method of cow leather containing bioactive components |
| CN114085933A (en) * | 2021-11-29 | 2022-02-25 | 河北省皮革研究院 | Low-chromium high-absorption tanning method |
| CN114410856A (en) * | 2022-02-24 | 2022-04-29 | 四川大学 | Chromium-free combined main tanning technology for ecological leather |
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