CN114410854A - High-temperature-dyeable ecological fur chrome-free combined main tanning process - Google Patents

Abstract

The invention belongs to the technical field of leather processing, and discloses a chromium-free combined main tanning process for ecological fur that can be dyed at high temperature. TWLZ tanning agent has excellent dispersing and fixing effect on collagen fibers, so that the vegetable tanning agent can penetrate into the skin evenly under the conditions of small dosage, high liquid ratio and weak mechanical action, and combine with TWLZ tanning agent and bind to the skin collagen fibers. The macromolecular cross-linked network structure is formed in the middle, which produces a synergistic tanning effect and endows the tanned fur with sufficient humidity and heat stability to meet the needs of high-temperature dyeing. The method does not need to use chromium retanning which is necessary before high-temperature dyeing, effectively avoids the generation of chromium-containing wastewater, and is conducive to promoting the green development of the leather industry.

Description

High temperature dyeable ecological fur chrome-free combined with main tanning process

technical field

The invention relates to the technical field of leather processing, in particular to a chrome-free combined main tanning process for ecological fur that can be dyed at high temperature.

Background technique

Dyeing is one of the important processes in fur processing. By dyeing, the variety of fur colors can be increased and the added value of the finished product can be increased. However, there is a dense layer of scales on the surface of the fur coat, which needs to be fully opened under high temperature conditions, and the dye can enter the wool fiber to complete the dyeing. Therefore, fur needs to be dyed under high temperature conditions.

At present, before dyeing fur, chrome retanning is usually required to improve the wet heat stability of fur, so that it can meet the requirements of high temperature dyeing. However, the process technology based on chrome tanning will inevitably produce a large amount of chrome-containing wastewater. The national standard stipulates that the total chromium emission limit of workshop or production facility wastewater discharge outlet is 1.5 mg/L. To meet this requirement, wastewater treatment is difficult and costly. Therefore, the development of a chrome-free tanning process for ecological fur that can be dyed at high temperature is of great significance for improving the sustainability of the fur industry.

Chrome-free tanning technology mainly includes non-chrome metal tanning technology and organic tanning technology. Non-chrome metal tanning agents have a certain tanning effect, but the cross-linking effect on collagen fibers is far less than that of chrome tanning agents, resulting in low shrinkage temperature of tanned furs. A rigid state that has no use value. Vegetable tanning technology is a typical organic tanning technology. The tannin extract used in it has the advantages of wide source, renewable, free formaldehyde-free, etc. It is an environmentally friendly tanning agent. However, tannin extract is easy to form an aggregated structure in an aqueous solution, and it is difficult to evenly penetrate into the skin under the fur tanning process system with large liquid ratio and weak mechanical action. In addition, the cross-linking effect of tannin extract on collagen fibers is also weak, which makes vegetable tanned fur not resistant to high temperature and difficult to meet the requirements of high temperature dyeing. It can be seen that it is difficult for a single tanning agent to give fur sufficient moisture and heat stability to meet the requirements of high temperature dyeing.

In view of this, the present invention is proposed.

SUMMARY OF THE INVENTION

Aiming at the defects of low shrinkage temperature and weak high temperature tolerance of tanning fur in the existing chrome-free tanning technology, the purpose of the present invention is to provide a chrome-free combined tanning process for ecological fur that can be dyed at high temperature, which is characterized by the shrinkage temperature of tanned fur. High leather yield and soft leather after high and high temperature dyeing.

To achieve the above object, the technical scheme adopted in the present invention is:

The ecological fur that can be dyed at high temperature is chrome-free combined with the main tanning process, using pickled and softened fur as raw material, first tanned with TWLZ tanning agent, and then tanned with tannin extract.

Preferably, the added amount of the TWLZ tanning agent is 10-30 g/L based on the volume of water added for tanning the fur.

Preferably, the tanning of the TWLZ tanning agent is that after penetrating the TWLZ tanning agent for 3.5-9 hours, the alkali is extracted to pH 3.5-4.0, and combined at 35-42° C. for 1-4 hours.

Preferably, in terms of the volume of water added to the tanning fur, the added amount of the tannin extract is 8-20 g/L.

Preferably, the tannin extract is permeated at pH 5.0-6.5 for 3.5-7.5 h, then lowered to pH 3.5-4.0, and combined at 32-38° C. for 0.5-1 h.

Preferably, the tannin extract is light-colored tannin extract, including but not limited to any one or more of tara tannin extract, light-colored chestnut tannin extract, light-colored wattle bark tannin extract and light-colored quebracho tannin extract.

Preferably, the pickled and softened fur includes, but is not limited to, any one of pickled and softened sheep fur, lamb fur, Tuscan sheep fur and tan sheep fur.

Preferably, before tanning with the TWLZ tanning agent, the step of adding a nonionic degreasing agent and a grease dispersant to the pickling softened fur, and rotating or paddling for 20-40 min at 30-35°C;

Preferably, based on the volume of water added to the tanning fur, the added amount of the nonionic degreaser is 0.5-2 g/L, and the added amount of the oil dispersant is 0.5-3 g/L.

Preferably, alkali extraction is performed on the solution with an alkali extraction agent, and the alkali extraction agent includes but is not limited to any one or more of sodium bicarbonate, sodium carbonate, magnesium oxide and automatic alkali extraction agent.

The present invention also provides an ecological fur that can be dyed at high temperature by adopting any of the above-mentioned chromium-free and main tanning processes.

Compared with the prior art, the present invention has the following beneficial effects:

(1) The TWLZ tanning agent in the present invention has excellent dispersing and fixing effects on collagen fibers, so that the tannin extract can evenly penetrate into the leather under the condition of high liquid ratio and weak mechanical action. Technical effects that are difficult to achieve by tanning technology.

(2) In the present invention, TWLZ and tannin extract can form a macromolecular cross-linked network structure in the skin collagen fibers, which significantly improves the cross-linking effect of the tanning agent on the collagen fibers and produces a synergistic tanning effect. Compared with the main tanning method of tannin extract, it can endow the tanned fur with higher humidity and heat stability.

(3) Compared with the existing chrome-free tanning system, the "TWLZ + tannin extract" combined tanning system provided by the present invention can obtain tanned furs with high shrinkage temperature and strong high temperature tolerance only through the main tanning process, which can meet the requirements of non-chrome tanning. The demand for high-temperature dyeing of chrome, high leather yield, soft leather, no need to use chrome retanning, effectively avoid the generation of chrome-containing wastewater.

Detailed ways

In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the specific embodiments. It should be understood that these descriptions are exemplary only and are not intended to limit the scope of the invention. Also, in the following description, descriptions of well-known structures and techniques are omitted to avoid unnecessarily obscuring the concepts of the present invention. If the specific conditions are not indicated in the examples, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used without the manufacturer's indication are conventional products that can be purchased from the market.

The embodiment provided by the present invention is as follows: the ecological fur that can be dyed at high temperature is chrome-free combined with the main tanning process, using pickling and softening fur as raw material, first tanning with TWLZ tanning agent, and then tanning with tannin extract.

The existing non-chromium metal tanning agents and tannin extract tanned furs all have the defects of low shrinkage temperature and weak high temperature tolerance, and it is difficult to meet the requirements of chrome-free high temperature dyeing of ecological furs. The applicant found in the experiment that the combined tanning technology of TWLZ and tannin extract can significantly improve the wet-heat stability of tanned fur, so that it can meet the requirements of high temperature dyeing. The principle is: TWLZ tanning agent is a kind of modified polysaccharide and aluminum. - The chromium-free complex tanning agent formed by the coordination of zirconium salts has stronger tanning properties than conventional aluminum-zirconium salts, and has excellent dispersion and fixation effects on collagen fibers, so that tannin extract can penetrate into the skin evenly, not only It can form multi-point hydrogen bonds with skin collagen, and can also form coordination binding with metal ions in TWLZ, thereby forming a macromolecular cross-linked network structure in the skin collagen fiber network, which significantly improves the cross-linking of tanning agents to collagen fibers. The combined action produces a synergistic tanning effect, which leads to the fact that the tanned fur will not shrink under high-temperature dyeing conditions, and finally achieves the effect of chrome-free high-temperature dyeing.

In some preferred embodiments, the pickled-softened fur includes, but is not limited to, any of pickled-softened sheep fur, lamb fur, Tuscan sheep fur and tan sheep fur.

In some specific embodiments, the amount of the TWLZ tanning agent added is 10-30 g/L based on the volume of water added to the tanning fur, that is, for every 1 L of water added to the tanning fur, the amount of the TWLZ tanning agent added is 10 g/L. -30 g, the TWLZ tanning agent in this concentration range can realize the present invention.

The tanning of the TWLZ tanning agent is that after penetrating the TWLZ tanning agent in the pickling softened fur for 3.5-9 hours, the alkali is elevated to pH 3.5-4.0, and combined at 35-42° C. for 1-4 hours.

In order to remove the grease from the pickled and softened fur, before adding the TWLZ tanning agent, the step of adding a nonionic degreasing agent and a grease dispersant to the pickled and softened fur may also be included to react. In some preferred embodiments, the nonionic degreasing agent is added in an amount of 0.5-2 g/L, and the oil and fat agent is added in an amount of 0.5-3 g/L based on the volume of water added to the tanning fur.

In some specific embodiments, the tanning method of TWLZ tanning agent can be: placing the pickled softened fur obtained by conventional technology in a drum or a slot, adding water with a liquid ratio of 5-20, 50-80 g/ L sodium chloride, 0.5-2 g/L nonionic degreaser and 0.5-3 g/L grease dispersant, the temperature is controlled at 30-35 ℃, after rotating or paddling for 20-40 min, add 10- 30 g/L of TWLZ tanning agent, turning or paddling for 2-4 h, stopping for 0-1 h, turning or paddling for 1-2 h, stopping for 0-1 h, then repeating every hour of turning or paddling for 5 min A total of 8 operations were performed. After the pH was 3.5-4.0 with an alkali-extracting agent, the temperature was raised to 35-42 °C, rotated or paddled for 1-3 h, stopped for 0-1 h, and drained.

Wherein, the tanning liquor is subjected to alkali extraction with an alkali extraction agent, and the alkali extraction agent includes but is not limited to any one or more of sodium bicarbonate, sodium carbonate, magnesium oxide and automatic alkali extraction agent.

In terms of the volume of water added by the tanning fur, the addition of the tannin extract is 8-20 g/L, that is, every time the tanning fur adds 1 L of water, the addition of the tannin extract is 8-20 g. Tannin extract can realize the present invention.

The tannin extract tanning is to infiltrate 3.5-7.5 h at pH 5.0-6.5, lower the pH to 3.5-4.0, and combine at 32-38°C for 0.5-1 h, that is, to soften the pickled fur after tanning with TWLZ tanning agent. This tanning process is carried out.

It should be noted that the reagents for adjusting the pH of the solution are all conventional reagents in the art, and all reagents that can adjust the pH of the solution to the target value should belong to the protection scope of the present invention.

In some preferred embodiments, in order not to affect the color of the tanned fur, the tannin extract is preferably light-colored tannin extract, including but not limited to tara tannin extract, light-colored chestnut tannin extract, light-colored wattle bark tannin extract and light-colored tannin extract Any one or more of quebracho tannin extracts.

In order to further remove the grease in the TWLZ tanned fur, before adding the tannin extract, the step of adding a grease dispersant to the pickled and softened fur tanned with the TWLZ tanning agent may also be included for reaction. In some preferred embodiments, based on the volume of water added to the tanning fur, the added amount of the oil and fat component is 0.5-2 g/L.

As in some specific embodiments, the tanning method of tannin extract can be as follows: adding water with a liquid ratio of 5-20, 0.5-2 g/L oil dispersant and 1-3 g/L in a drum or a trough of sodium formate, control the temperature of the bath to 35-42°C, increase the pH of the bath to 5.0-6.0 with baking soda, turn or paddle for 1-2 h, and drain; add water with a liquid ratio of 5-20 to control the bath The temperature is 32-38℃, add 2-5 g/L of sulfated fatliquoring agent and 8-20 g/L tannin extract, turn or paddle for 2-4 h, stop for 0-1 h, turn or paddle 1-2 h, then repeat the operation of turning or paddling for 10 min 3 times per hour, adjust the pH of the bath solution to 3.5-4.0 with formic acid, turn or paddle for 0.5-1 h, peel out the skin, and obtain a high-temperature dyeing ecological Chrome-free tanned fur.

In order to better understand the technical solution provided by the present invention, the following describes the chrome-free combined main tanning process and performance test of the eco-leather provided by the above-mentioned embodiments of the present invention with a plurality of specific examples.

In the following examples and comparative examples, the measuring method of tanning fur shrinkage temperature is:

The tanned fur quilt is removed with a razor, leaving the skin. The shrinkage temperature of the skin was measured by a shrinkage thermometer to characterize the wet heat stability of the tanned fur.

In the following examples and comparative examples, the assay method of dyed fur yield is:

The tanned fur is dyed at high temperature according to the conventional dyeing and finishing process to obtain dyed fur. The area of tanned and dyed furs was measured separately using a square area board (1cm ² /square). The calculation formula of the leather yield of dyed fur is shown in formula (1). The greater the leather yield, the smaller the area shrinkage during the high-temperature dyeing process, and the stronger the temperature resistance of the tanned fur.

（1）

(1)

In the following examples and comparative examples, the method for measuring the softness of dyed fur is:

The dyed fur quilt is removed with a razor, leaving the hide. The softness of the veneer was measured by a softness tester.

Part of the material information used in the specific embodiments of the present invention may be as follows:

Non-ionic degreasing agent: FG-B produced by Sichuan Dawei Technology Co., Ltd., DW produced by Sichuan Desaier New Material Technology Co., Ltd., TJ-A124 and TJ-A136 produced by Sichuan Tingjiang New Material Co., Ltd.;

Oil dispersant: SAF produced by Derui Leather Technology (Qingdao) Co., Ltd.;

TWLZ tanning agent: Sichuan Tingjiang New Materials Co., Ltd.;

Automatic alkali extraction agent: MGO produced by Stahl Fine Coatings (Suzhou) Co., Ltd., MO produced by Sichuan Desaier New Material Technology Co., Ltd. and TJ-A511 produced by Sichuan Tingjiang New Material Co., Ltd.;

Sulfated fatliquor: Kurtalin ABM, Sintoil 88 and Sintoil CH produced by Silvateam, Italy;

Tara tannin extract: TJ-R231 produced by Sichuan Tingjiang New Materials Co., Ltd.;

Light-colored chestnut tannin extract: Dulcotan Special produced by Silvateam, Italy;

Light-colored wattle bark tannin extract: Supersol Light produced by Brazil's Seta Company;

Light-colored quebratus tannin extract: Indusol Atd produced by Silvateam, Italy.

Example 1

High temperature dyeable ecological fur chrome-free combined with main tanning process:

(1) Put the pickled and softened sheep fur obtained by the conventional process in a rotating drum, add water with a liquid ratio of 5, 50 g/L sodium chloride, 1.2 g/L nonionic degreaser FG-B and 1.8 g/L of oil dispersant SAF, the temperature was controlled at 30 °C, after 40 min of rotation, 20 g/L of TWLZ tanning agent was added, rotated for 4 h, stopped for 1 h, rotated for 1 h, stopped for 0.5 h, and then repeated every The operation was rotated for 5 min for a total of 8 times per hour. After alkali extraction with magnesium oxide to pH 3.5, the temperature was raised to 35 °C, rotated for 2 h, stopped for 1 h, and drained;

(2) Add water with a liquid ratio of 13, 0.5 g/L of oil dispersant SAF and 2 g/L of sodium formate to the drum, control the temperature of the bath to 42°C, and increase the pH of the bath to 5.5 with baking soda. Rotate for 1.5 h, drain; add water with a liquid ratio of 5, control the bath temperature to 38 °C, add 3.5 g/L sulfated fatliquoring agent Kurtalin ABM and 14 g/L light-colored wattle bark tannin extract Supersol Light, turn for 4 h, stop for 1 h, turn for 1.5 h, and then repeat the operation of turning 10 min every hour 3 times. After adjusting the pH of the bath solution to 3.8 with formic acid, turn it for 0.5 h, and peel off the skin to obtain an eco-free dye that can be dyed at high temperature. Chrome tanned fur.

It was determined that the shrinkage temperature of the tanned fur was 103.2 °C, the leather yield of the fur after high temperature dyeing was 99.2%, and the softness was 7.2 mm. The test results are shown in Table 1.

Comparative Example 1

The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 only adopts the TWLZ tanning agent of 20 g/L to carry out tanning, and does not adopt tannin extract to carry out tanning, and the detailed processing steps are:

The pickling and softening sheep fur obtained by the conventional process was placed in a rotating drum, and water with a liquid ratio of 5, 50 g/L sodium chloride, 1.2 g/L nonionic degreaser FG-B and 1.8 g/L were added. L of oil dispersant SAF, the temperature was controlled at 30 °C, after 40 min of rotation, 20 g/L of TWLZ tanning agent was added, rotated for 4 h, stopped for 1 h, rotated for 1 h, stopped for 0.5 h, and then repeated every hour for 5 hours. The operation was carried out 8 times for min. After alkali extraction with magnesium oxide to pH 3.5, the temperature was raised to 35 °C, rotated for 2 h, stopped for 1 h, and the skin was extracted to obtain chrome-free tanned fur.

It was determined that the shrinkage temperature of the tanned fur was 81.4 °C, the yield of the fur after high temperature dyeing was 73.2%, and the softness was 4.3 mm. The test results are shown in Table 1.

Comparative Example 2

The difference between Comparative Example 2 and Example 1 is that Comparative Example 2 only adopts the TWLZ tanning agent of 34 g/L to carry out tanning, and does not adopt tannin extract to carry out tanning, and the detailed processing steps are:

The pickling and softening sheep fur obtained by the conventional process was placed in a rotating drum, and water with a liquid ratio of 5, 50 g/L sodium chloride, 1.2 g/L nonionic degreaser FG-B and 1.8 g/L were added. L of oil dispersant SAF, the temperature was controlled at 30 °C, after 40 min of rotation, 34 g/L of TWLZ tanning agent was added, rotated for 4 h, stopped for 1 h, rotated for 1 h, stopped for 0.5 h, and then repeated 5 rotations per hour. The operation was carried out 8 times for min. After alkali extraction with magnesium oxide to pH 3.5, the temperature was raised to 35 °C, rotated for 2 h, stopped for 1 h, and the skin was extracted to obtain chrome-free tanned fur.

It was determined that the shrinkage temperature of the tanned fur was 85.8 °C, the yield of the fur after high temperature dyeing was 74.3%, and the softness was 4.5 mm. The test results are shown in Table 1.

Comparative Example 3

The difference between Comparative Example 3 and Example 1 is that Comparative Example 3 only adopts the tannin extract of 14 g/L to carry out tanning, and does not adopt TWLZ tanning agent to carry out tanning, and the detailed processing steps are:

The pickled and softened sheep fur obtained by the conventional process was placed in a rotating drum, water with a liquid ratio of 13, 0.5 g/L of oil dispersant SAF and 2 g/L of sodium formate were added, and the temperature of the bath was controlled to be 42°C. Raise the pH of the bath solution to 5.5 with baking soda, turn it for 1.5 h, and drain; add water with a liquid ratio of 5, control the bath temperature to 38 °C, add 3.5 g/L sulfated fatliquoring agent Kurtalin ABM and 14 g/L L of light-colored wattle bark tannin extract Supersol Light, rotate for 4 h, stop for 1 h, rotate for 1.5 h, then repeat the operation of rotating 10 min per hour 3 times, adjust the pH of the bath with formic acid to 3.8, rotate for 0.5 h, The hides are removed to obtain chrome-free tanned furs.

It was determined that the shrinkage temperature of the tanned fur was 73.4 °C, the yield of the fur after high temperature dyeing was 68.5%, and the softness was 4.1 mm. The test results are shown in Table 1.

Comparative Example 4

The difference between Comparative Example 4 and Example 1 is that Comparative Example 2 only adopts the tannin extract of 34 g/L to carry out tanning, and does not adopt TWLZ tanning agent to carry out tanning, and the detailed processing steps are:

The pickled and softened sheep fur obtained by the conventional process was placed in a rotating drum, water with a liquid ratio of 13, 0.5 g/L of oil dispersant SAF and 2 g/L of sodium formate were added, and the temperature of the bath was controlled to be 42°C. Raise the pH of the bath solution to 5.5 with baking soda, turn it for 1.5 h, and drain; add water with a liquid ratio of 5, control the bath temperature to 38 °C, add 3.5 g/L sulfated fatliquoring agent Kurtalin ABM and 14 g/L L of light-colored wattle bark tannin extract Supersol Light, rotate for 4 h, stop for 1 h, rotate for 1.5 h, then repeat the operation of rotating 10 min per hour 3 times, adjust the pH of the bath with formic acid to 3.8, rotate for 0.5 h, The hides are removed to obtain chrome-free tanned furs.

It was determined that the shrinkage temperature of the tanned fur was 77.3°C, the leather yield of the fur after dyeing at high temperature was 72.3%, and the softness was 4.2 mm. The test results are shown in Table 1.

Comparative Example 5

The difference between Comparative Example 5 and Example 1 is that in Comparative Example 5, a conventional aluminum-zirconium tanning agent was used to replace the TWLZ tanning agent in an equal amount, and the remaining operations were exactly the same as those in Example 1. The detailed process steps of Comparative Example 5 are:

(1) Put the pickled and softened sheep fur obtained by the conventional process in a rotating drum, add water with a liquid ratio of 5, 50 g/L sodium chloride, 1.2 g/L nonionic degreaser FG-B and 1.8 g/L oil dispersant SAF, the temperature is controlled at 30 °C, after rotating for 40 min, add 20 g/L aluminum-zirconium tanning agent, rotate for 4 h, stop for 1 h, rotate for 1 h, stop for 0.5 h, and then Repeat the operation of rotating for 5 min per hour for a total of 8 times. After alkali extraction with magnesium oxide to pH 3.5, the temperature is raised to 35 °C, rotated for 2 h, stopped for 1 h, and drained;

(2) Add water with a liquid ratio of 13, 0.5 g/L of oil dispersant SAF and 2 g/L of sodium formate to the drum, control the temperature of the bath to 42°C, and increase the pH of the bath to 5.5 with baking soda. Rotate for 1.5 h, drain; add water with a liquid ratio of 5, control the bath temperature to 38 °C, add 3.5 g/L sulfated fatliquoring agent Kurtalin ABM and 14 g/L light-colored wattle bark tannin extract Supersol Light, turn for 4 h, stop for 1 h, turn for 1.5 h, and then repeat the operation of turning 10 min every hour 3 times. After adjusting the pH of the bath solution to 3.8 with formic acid, turn it for 0.5 h, and peel off the skin to obtain an eco-free dye that can be dyed at high temperature. Chrome tanned fur.

It was determined that the shrinkage temperature of the tanned fur was 92.0 °C, the leather yield of the fur after high temperature dyeing was 90.7%, and the softness was 6.1 mm. The test results are shown in Table 1.

Comparative Example 6

The difference between Comparative Example 6 and Example 1 is that in Comparative Example 6, the equivalent amount of synthetic tanning agent was used to replace tannin extract, and the remaining operations were exactly the same as in Example 1. The detailed process steps of Comparative Example 6 are:

(1) Put the pickled and softened sheep fur obtained by the conventional process in a rotating drum, add water with a liquid ratio of 5, 50 g/L sodium chloride, 1.2 g/L nonionic degreaser FG-B and 1.8 g/L of oil dispersant SAF, the temperature was controlled at 30 °C, after 40 min of rotation, 20 g/L of TWLZ tanning agent was added, rotated for 4 h, stopped for 1 h, rotated for 1 h, stopped for 0.5 h, and then repeated every The operation was rotated for 5 min for a total of 8 times per hour. After alkali extraction with magnesium oxide to pH 3.5, the temperature was raised to 35 °C, rotated for 2 h, stopped for 1 h, and drained;

(2) Add water with a liquid ratio of 13, 0.5 g/L of oil dispersant SAF and 2 g/L of sodium formate to the drum, control the temperature of the bath to 42°C, and increase the pH of the bath to 5.5 with baking soda. Rotate for 1.5 h, drain; add water with a liquid ratio of 5, control the bath temperature to 38 °C, add 3.5 g/L sulfated fatliquor Kurtalin ABM and 14 g/L synthetic tanning agent, rotate for 4 h, stop For 1 h, rotate for 1.5 h, and then repeat the operation of rotating for 10 min every hour 3 times. After adjusting the pH of the bath solution to 3.8 with formic acid, rotate for 0.5 h, and the hides are produced to obtain ecological chrome-free tanned furs that can be dyed at high temperature.

It was determined that the shrinkage temperature of the tanned fur was 90.8 °C, the yield of the fur after high temperature dyeing was 90.2%, and the softness was 5.9 mm. The test results are shown in Table 1.

Comparative Example 7

The difference between Comparative Example 7 and Example 1 is that in Comparative Example 7, double the amount of synthetic tanning agent was used to replace tannin extract, and the remaining operations were exactly the same as in Example 1. The detailed process steps of Comparative Example 7 are:

(1) Put the pickled and softened sheep fur obtained by the conventional process in a rotating drum, add water with a liquid ratio of 5, 50 g/L sodium chloride, 1.2 g/L nonionic degreaser FG-B and 1.8 g/L of oil dispersant SAF, the temperature was controlled at 30 °C, after 40 min of rotation, 20 g/L of TWLZ tanning agent was added, rotated for 4 h, stopped for 1 h, rotated for 1 h, stopped for 0.5 h, and then repeated every The operation was rotated for 5 min for a total of 8 times per hour. After alkali extraction with magnesium oxide to pH 3.5, the temperature was raised to 35 °C, rotated for 2 h, stopped for 1 h, and drained;

(2) Add water with a liquid ratio of 13, 0.5 g/L of oil dispersant SAF and 2 g/L of sodium formate to the drum, control the temperature of the bath to 42°C, and increase the pH of the bath to 5.5 with baking soda. Rotate for 1.5 h, drain; add water with a liquid ratio of 5, control the bath temperature to 38 °C, add 3.5 g/L sulfated fatliquoring agent Kurtalin ABM and 28 g/L synthetic tanning agent, rotate for 4 h, stop For 1 h, rotate for 1.5 h, and then repeat the operation of rotating for 10 min every hour 3 times. After adjusting the pH of the bath solution to 3.8 with formic acid, rotate for 0.5 h, and the hides are produced to obtain ecological chrome-free tanned furs that can be dyed at high temperature.

It was determined that the shrinkage temperature of the tanned fur was 95.9 °C, the yield of the fur after high temperature dyeing was 92.1%, and the softness was 6.4 mm. The test results are shown in Table 1.

According to the test results of Example 1 and Comparative Examples 1-7, it can be seen that in Example 1, TWLZ was used with tannin extract for combined tanning, and the shrinkage temperature of the tanned fur was as high as 103.2°C. After high-temperature dyeing, there was almost no shrinkage. It is 99.2%, and the dyed fur also maintains good sensory properties, and the softness is as high as 7.2 mm; in Comparative Example 1, 20 g/L TWLZ was used for tanning, and the shrinkage temperature of the tanned fur was 81.4 °C, and the leather yield after high-temperature dyeing was only It is 73.2%, the shrinkage is obvious, and the dyed fur is in a hard state, and the softness is only 4.3 mm; in Comparative Example 2, 34 g/L TWLZ was used for tanning, and the shrinkage temperature of the tanned fur was 85.8 °C, and the leather was obtained after high temperature dyeing. The rate is only 74.3%, the shrinkage is obvious and the dyed fur is in a stiff state, and the softness is only 4.5 mm; Comparative Example 3 was tanned with 14 g/L tannin extract, and the shrinkage temperature of the tanned fur was 73.4 ℃, and it was dyed at high temperature. The after-leather rate is only 68.5%, the shrinkage is also obvious, and the dyed fur is in a hard state, with a softness of only 4.1 mm; Comparative Example 4 was tanned with 34 g/L tannin extract, and the shrinkage temperature of the tanned fur was 77.3 °C , the leather yield after high temperature dyeing is only 72.3%, the shrinkage is also obvious, and the dyed fur is in a hard state, with a softness of only 4.2 mm; in Comparative Example 5, conventional aluminum zirconium tanning agent and tannin extract were used for tanning, and the tanned fur was The shrinkage temperature was 92.0 °C, the leather yield after high-temperature dyeing was 90.7%, and the softness of the dyed fur was 6.1 mm; in Comparative Example 6, the same amount of synthetic tanning agent was used to replace tannin extract and TWLZ for combined tanning, and the shrinkage temperature of the tanned fur was 90.8 ℃, the leather yield after high temperature dyeing was 90.2%, and the softness of the dyed fur was 5.9 mm; in Comparative Example 7, 2 times of synthetic tanning agent was used to replace tannin extract and combined tanning with TWLZ, the shrinkage temperature of the tanned fur was 95.9 ℃, After high temperature dyeing, the leather yield was 92.1%, and the softness of dyed fur was 6.4 mm.

The shrinkage temperature of pickling and softening sheep fur is 62.6°C. After the combined tanning of 20 g/L TWLZ and 14 g/L tannin extract in Example 1, the shrinkage temperature of the tanned fur reaches 103.2°C, indicating that "TWLZ + tannin extract" The shrinkage temperature increase (ΔTs) was 40.6°C. The shrinkage temperature of the TWLZ tanned fur at 20 g/L in Comparative Example 1 was 81.4°C, and the ΔTs was 18.8°C. The shrinkage temperature of the tannin extract tanned fur at 14 g/L in Comparative Example 3 was 73.4°C, and the ΔTs was 10.8°C. It can be seen that the ΔTs of "TWLZ + tannin extract" has exceeded the sum of TWLZ and tannin extract ΔTs, that is, 40.6°C>(18.8°C+10.8°C), indicating that the combination of "TWLZ+ tannin extract" used in the present invention produces a significant effect on the tanning process. synergistic tanning effect. The shrinkage temperature of the 34 g/L TWLZ tanned fur in Comparative Example 2 was 85.8°C, and the ΔTs was 23.2°C. The shrinkage temperature of the tannin extract tanned fur at 34 g/L in Comparative Example 4 was 77.3°C, and the ΔTs was 14.7°C. Similarly, the ΔTs of “TWLZ+ tannin extract” has exceeded the sum of TWLZ and tannin extract ΔTs, that is, 40.6°C>(23.2°C+14.7°C), indicating that under the same amount of tanning agent, the “TWLZ+ tannin extract” used in the present invention "The combined tanning process still produced a significant synergistic tanning effect.

The shrinkage temperature and temperature resistance of Example 1 tanned fur are better than Comparative Example 5 in all directions, illustrating that conventional aluminum-zirconium tanning agent can not replace TWLZ tanning agent to obtain the high shrinkage temperature and strong temperature resistance that want to be realized in the present invention. Effect. This is mainly because the conventional aluminum-zirconium tanning agent does not contain modified polysaccharide ligands, so the dispersing and fixing ability of the formed complex to collagen fibers is not as good as that of the TWLZ tanning agent, which makes the tannin extract difficult to penetrate uniformly. In addition, the shrinkage temperature and temperature resistance of the tanned fur of Example 1 are also better than those of Comparative Examples 6 and 7, indicating that even if the synthetic tanning agent of 2 times the amount is adopted, the technical effect desired to be achieved in the present invention cannot be obtained in place of tannin extract. This is mainly due to the fact that the synthetic tanning agent has a small molecular weight and few phenolic hydroxyl groups, and it is difficult to form a macromolecular cross-linked network structure after coordinating with TWLZ. From the results of the above examples and comparative examples, it can be shown that the synergistic tanning process of "TWLZ + tannin extract" adopted in the present invention has significant progress compared with the prior art, resulting in unexpected effects.

Table 1 Test results

。

.

Example 2

High temperature dyeable ecological fur chrome-free combined with main tanning process:

(1) The pickled and softened lamb fur obtained by the conventional process was placed in a groove, and water with a liquid ratio of 13, 80 g/L of sodium chloride, 2 g/L of nonionic degreaser DW and 0.5 g/L of water were added. L of oil dispersant SAF, the temperature was controlled at 32 °C, after 30 min of paddling, 10 g/L of TWLZ tanning agent was added, paddled for 4.5 h, and then repeated the operation of paddling 5 min every hour for a total of 8 times, with carbonic acid After alkaline extraction with sodium hydrogen to pH 4.0, the temperature was raised to 42 °C, paddled for 1 h, and drained;

(2) Add water with a liquid ratio of 20, 2 g/L of grease dispersant SAF and 1 g/L of sodium formate to the groove, control the temperature of the bath to 35°C, and increase the pH of the bath to 5.0 with baking soda. Swipe for 2 h, drain; add water with a liquid ratio of 20, control the bath temperature to 32 °C, add 2 g/L sulfated fatliquor Sintoil 88 and 20 g/L tara tannin extract TJ-R231 , paddling for 5 hours, and then repeated the operation of paddling for 10 min every hour 3 times. After adjusting the pH of the bath solution to 3.5 with formic acid, paddling for 0.8 hours, the leather was peeled, and the ecological chrome-free tanned fur that could be dyed at high temperature was obtained.

It was determined that the shrinkage temperature of the tanned fur was 99.7℃, the leather yield of the fur after high temperature dyeing was 98.6%, and the softness was 7.0 mm.

Example 3

High temperature dyeable ecological fur chrome-free combined with main tanning process:

(1) Put the pickled and softened Tuscan sheep fur obtained by the conventional process in a rotating drum, add water with a liquid ratio of 20, 65 g/L sodium chloride, and 0.5 g/L nonionic degreaser TJ-A124 and 3 g/L oil dispersant SAF, the temperature was controlled at 35 °C, after rotating for 20 min, 30 g/L TWLZ tanning agent was added, rotating for 2 h, stopping for 0.5 h, rotating for 2 h, stopping for 1 h After that, the operation of rotating for 5 min per hour was repeated for a total of 8 times. After the pH was adjusted to 3.8 with sodium carbonate, the temperature was raised to 38 °C, rotated for 3 h, stopped for 0.5 h, and drained;

(2) Add water with a liquid ratio of 5, 1.2 g/L of oil dispersant SAF and 3 g/L of sodium formate to the drum, control the temperature of the bath to 38°C, and increase the pH of the bath to 6.0 with baking soda. Turn for 1 h, drain; add water with a liquid ratio of 13, control the bath temperature to 35 °C, add 5 g/L of sulfated fatliquoring agent Sintoil CH and 8 g/L of light-colored chestnut tannin extract DulcotanSpecial, rotate 2 h, stop for 0.5 h, rotate for 1 h, and then repeat the operation of rotating for 10 min every hour for 3 times. After adjusting the pH of the bath solution to 4.0 with formic acid, rotate for 1 h, and peel off the leather to obtain an ecological chrome-free tanned fur that can be dyed at high temperature. .

It was determined that the shrinkage temperature of the tanned fur was 105.9℃, the leather yield of the fur after high temperature dyeing was 99.4%, and the softness was 7.4 mm.

Example 4

High temperature dyeable ecological fur chrome-free combined with main tanning process:

(1) Put the pickled and softened tan sheep fur obtained according to the conventional process in a slot, and add water with a liquid ratio of 20, 65 g/L sodium chloride, 1.2 g/L nonionic degreaser TJ-A126 and 0.5 g/L of oil dispersant SAF, the temperature was controlled at 30 °C, after 20 min of paddling, 30 g/L of TWLZ tanning agent was added, paddled for 4 h, stopped for 0.5 h, paddled for 1 h, and repeated every hour thereafter The operation of paddling for 5 min was carried out 8 times in total. After alkali extraction with automatic alkali extraction agent MGO to pH 3.8, the temperature was raised to 38 °C, paddled for 3 hours, stopped for 0.5 hours, and drained;

(2) Add water with a liquid ratio of 13, 2 g/L of oil dispersant SAF and 2 g/L of sodium formate to the scribing groove, control the temperature of the bath to 38°C, and increase the pH of the bath to 5.5 with baking soda. Swipe for 1 h, drain; add water with a liquid ratio of 20, control the bath temperature to 38 °C, add 3.5 g/L sulfated fatliquoring agent Kurtalin ABM and 14 g/L light-colored quercetin extract IndusloAtd , paddling for 3 h, and then repeated the operation of paddling for 10 min every hour for 3 times. After adjusting the pH of the bath solution to 4.0 with formic acid, paddling for 1 h, the skin was peeled, and the ecological chrome-free tanned fur that could be dyed at high temperature was obtained.

It was determined that the shrinkage temperature of the tanned fur was 107.5℃, the leather yield of the fur after high temperature dyeing was 99.6%, and the softness was 7.5 mm.

Example 5

High temperature dyeable ecological fur chrome-free combined with main tanning process:

(1) Put the pickled and softened sheep fur obtained by the conventional process in a rotating drum, add water with a liquid ratio of 13, 80 g/L of sodium chloride, 2 g/L of nonionic degreaser FG-B and 1.8 g/L oil dispersant SAF, the temperature is controlled at 35 °C, after 30 min of rotation, add 10 g/L of TWLZ tanning agent, rotate for 4.5 h, stop for 1 h, and then repeat the operation of 5 min per hour for a total of 8 times , after alkali extraction with automatic alkali extraction agent MO to pH 4.0, the temperature was raised to 42 °C, rotated for 1 h, and the liquid was drained;

(2) Add water with a liquid ratio of 5, 0.5 g/L of oil dispersant SAF and 1 g/L of sodium formate to the drum, control the temperature of the bath to 35°C, and increase the pH of the bath to 5.0 with baking soda. Turn for 2 h, drain; add water with a liquid ratio of 5, control the bath temperature to 32 °C, add 2 g/L of sulfated fatliquoring agent Sintoil 88, 4 g/L of Tara tannin extract TJ-R231 and 4 g/L of light-colored chestnut tannin extract Dulcotan Special, rotate for 3 h, stop for 0.5 h, rotate for 2 h, then repeat the operation of rotating 10 min per hour 3 times, adjust the pH of the bath solution to 3.5 with formic acid, and rotate for 0.5 h , out of the hides to obtain ecological chrome-free tanned furs that can be dyed at high temperature.

It was determined that the shrinkage temperature of the tanned fur was 99.2°C, the leather yield of the fur after high temperature dyeing was 98.3%, and the softness was 6.8 mm.

Example 6

High temperature dyeable ecological fur chrome-free combined with main tanning process:

(1) The pickled and softened lamb fur obtained by the conventional process was placed in a slot, and water with a liquid ratio of 5, 50 g/L of sodium chloride, 0.5 g/L of nonionic degreaser DW and 3 g of water were added. /L of oil dispersant SAF, the temperature was controlled at 32 °C, after 40min of paddling, 20 g/L of TWLZ tanning agent was added, paddled for 2 h, paused for 1 h, paddled for 2 h, paused for 0.5 h, and repeated every The operation of paddling for 5 minutes was carried out for 8 times per hour. After the pH was 3.5 with the automatic alkali extraction agent TJ-A511, the temperature was raised to 35 °C, paddling for 2 hours, stopped for 1 hour, and drained;

(2) Add water with a liquid ratio of 20, 1.2 g/L of oil dispersant SAF and 3 g/L of sodium formate to the scribing groove, control the temperature of the bath to 42°C, and increase the pH of the bath to 5.0 with baking soda. Swipe for 1 h, drain; add water with a liquid ratio of 20, control the temperature of the bath to 32 °C, add 2 g/L of sulfated fatliquoring agent Sintoil CH, and 7 g/L of light-colored quebratus tannin extract Indusol Atd and 7 g/L of light-colored wattle bark tannin extract Supersol Light, paddled for 2 h, stopped for 1 h, paddled for 2 h, then repeated the operation of paddling for 10 min every hour 3 times, adjusted the pH of the bath with formic acid After reaching 3.8, paddling for 0.5 h, peeled out the hide, and obtained the ecological chrome-free tanned fur that can be dyed at high temperature.

It was determined that the shrinkage temperature of the tanned fur was 99.4℃, the leather yield of the fur after high temperature dyeing was 98.5%, and the softness was 6.9 mm.

Example 7

High temperature dyeable ecological fur chrome-free combined with main tanning process:

(1) Put the pickled and softened Tuscan sheep fur obtained by the conventional process in a rotating drum, add water with a liquid ratio of 5, 50 g/L of sodium chloride, and 2 g/L of nonionic degreaser TJ-A124 and 1.8 g/L oil dispersant SAF, the temperature is controlled at 32 °C, after 30 min of rotation, add 10 g/L of TWLZ tanning agent, rotate for 3 h, stop for 1 h, rotate for 2 h, stop for 1 h After that, the operation of rotating for 5 min per hour was repeated for 8 times. After alkali extraction with sodium bicarbonate and magnesium oxide to pH 3.5, the temperature was raised to 35 °C, rotated for 1 h, and the liquid was drained;

(2) Add water with a liquid ratio of 5, 1.2 g/L of oil dispersant SAF and 1 g/L of sodium formate to the drum, control the temperature of the bath to 42°C, and increase the pH of the bath to 5.0 with baking soda. Turn for 1 h, drain; add water with a liquid ratio of 20, control the bath temperature to 32 °C, add 2 g/L sulfated fatliquor Kurtalin ABM, 7 g/L Tara tannin extract TJ-R231 and 7 g/L of light-colored wattle bark tannin extract Supersol Light, rotate for 2 h, stop for 1 h, rotate for 2 h, and then repeat the operation of rotating 10 min per hour 3 times, adjust the pH of the bath solution to 3.8 with formic acid, and rotate After 0.5 h, the hides were peeled to obtain ecological chrome-free tanned furs that could be dyed at high temperature.

It was determined that the shrinkage temperature of the tanned fur was 99.4℃, the leather yield of the fur after high temperature dyeing was 98.5%, and the softness was 6.9 mm.

Example 8

High temperature dyeable ecological fur chrome-free combined with main tanning process:

(1) Put the pickled and softened tan sheep fur obtained by the conventional process in a slot, add water with a liquid ratio of 13, 80 g/L sodium chloride, 0.5 g/L nonionic degreaser TJ-A126 and 0.5 g/L of oil dispersant SAF, the temperature was controlled at 30 °C, after 20 min of paddling, 20 g/L of TWLZ tanning agent was added, paddled for 2 h, paused for 0.5 h, paddled for 1 h, paused for 0.5 h, After that, the operation of paddling for 5 min every hour was repeated for a total of 8 times. After the pH was adjusted to 3.8 with sodium carbonate and magnesium oxide, the temperature was raised to 38 °C, paddled for 2 h, stopped for 0.5 h, and drained;

(2) Add water with a liquid ratio of 20, 2 g/L of oil dispersant SAF and 3 g/L of sodium formate to the scribing groove, control the temperature of the bath to 35°C, and increase the pH of the bath to 6.0 with baking soda. Swipe for 1.5 h, drain; add water with a liquid ratio of 13, control the bath temperature to 35 °C, add 3.5 g/L of sulfated fatliquoring agent Sintoil 88, 4 g/L of light-colored chestnut tannin extract DulcotanSpecial and 4 g/L of light-colored wattle bark tannin extract Supersol Light, paddled for 3 hours, stopped for 0.5 hours, paddled for 1 hour, and then repeated the operation of paddling for 10 minutes every hour 3 times, and adjusted the pH of the bath solution to 3.5 with formic acid After stroking for 0.8 h, the hides were peeled to obtain ecological chrome-free tanned furs that could be dyed at high temperature.

It was determined that the shrinkage temperature of the tanned fur was 101.9℃, the leather yield of the fur after high temperature dyeing was 98.9%, and the softness was 7.1 mm.

Example 9

High temperature dyeable ecological fur chrome-free combined with main tanning process:

(1) The pickling and softening lamb fur obtained by the conventional process is placed in a rotating drum, and water with a liquid ratio of 20, 65 g/L sodium chloride, 1.2 g/L nonionic degreaser FG-B and 3 are added. g/L of oil dispersant SAF, the temperature was controlled at 35 °C, after 40 min of rotation, 30 g/L of TWLZ tanning agent was added, and the operation was rotated for 5.5 h. After that, the operation of rotating 5 min per hour was repeated for 8 times. After alkaline extraction with automatic alkali extraction agent TJ-A511 to pH 4.0, the temperature was raised to 42 °C, rotated for 3 h, stopped for 1 h, and drained;

(2) Add water with a liquid ratio of 13, 0.5 g/L of oil dispersant SAF and 2 g/L of sodium formate to the drum, control the temperature of the bath to 38°C, and increase the pH of the bath to 5.5 with baking soda. Turn for 2 h, drain; add water with a liquid ratio of 5, control the bath temperature to 38 °C, add 5 g/L sulfated fatliquoring agent Sintoil CH, 7 g/L light chestnut tannin extract DultosanSpecial, 7 g/L g/L light-colored quebrata tannin extract Indusol Atd and 6 g/L light-colored wattle bark tannin extract Supersol Light, rotate for 5.5 h, then repeat the operation of rotating 10 min per hour 3 times, adjust the pH of the bath with formic acid After reaching 4.0, turn it for 1 h to get the leather, and obtain the ecological chrome-free tanned fur that can be dyed at high temperature.

It was determined that the shrinkage temperature of the tanned fur was 108.4°C, the leather yield of the fur after high temperature dyeing was 99.7%, and the softness was 7.6 mm.

Example 10

High temperature dyeable ecological fur chrome-free combined with main tanning process:

(1) Place the pickled and softened sheep fur obtained by the conventional process in a groove, and add water with a liquid ratio of 13, 65 g/L sodium chloride, 2 g/L nonionic degreaser DW and 3 g/L L of oil dispersant SAF, the temperature was controlled at 35 °C, after 40 minutes of paddling, 30 g/L of TWLZ tanning agent was added, paddling for 3 h, paused for 0.5 h, paddled for 1.5 h, paused for 0.5 h, and repeated every hour thereafter. The operation of paddling for 5 min was carried out for 8 times. After the pH was 4.0 with sodium bicarbonate and the automatic alkali extraction agent MGO, the temperature was raised to 38 °C, paddling for 2 h, stopped for 0.5 h, and drained;

(2) Add water with a liquid ratio of 13, 1.2 g/L of oil dispersant SAF and 2 g/L of sodium formate into the scribed groove, control the temperature of the bath to 38°C, and increase the pH of the bath to 6.0 with baking soda. Swipe for 1 h, drain; add water with a liquid ratio of 13, control the bath temperature to 35 °C, add 5 g/L of sulfated fatliquor Sintoil 88, and 5 g/L of Tara tannin extract TJ-R231 , 5 g/L of light-colored chestnut tannin extract Dulcotan Special, 5 g/L of light-colored wattle bark tannin extract Supersol Light and 5 g/L of light-colored hardwood tannin extract Indusol Atd, paddling for 3 h, stopping for 0.5 h, paddled for 1 hour, and then repeated the operation of paddling for 10 min every hour 3 times. After adjusting the pH of the bath solution to 3.8 with formic acid, paddling for 0.8 h, the skin was peeled, and the ecological chrome-free tanned fur that could be dyed at high temperature was obtained.

It was determined that the shrinkage temperature of the tanned fur was 108.6℃, the leather yield of the fur after high temperature dyeing was 99.7%, and the softness was 7.6 mm.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand: It is still possible to modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. range.

Claims (10)

1. The non-chromium combined main tanning process for ecological fur capable of being dyed at high temperature features that pickling softened fur is used as material, and TWLZ tanning agent is used to tann the fur first and tanning extract is used to tann the fur.

2. The high-temperature dyeable ecological fur chrome-free combined main tanning process of claim 1, wherein the addition amount of the TWLZ tanning agent is 10-30 g/L based on the volume of water added for tanning the fur.

3. The high temperature dyeable eco-fur chrome-free combination main tanning process as claimed in claim 1, wherein the TWLZ tanning is carried out by penetrating TWLZ tanning agent for 3.5-9 h, extracting alkali to pH 3.5-4.0, and combining at 35-42 ℃ for 1-4 h.

4. The high-temperature dyeable ecological fur chrome-free combination main tanning process as claimed in claim 1, wherein the addition amount of the tannin extract is 8-20 g/L based on the volume of water added for tanning the fur.

5. The chrome-free combination main tanning process of ecological fur skin capable of high-temperature dyeing according to claim 1, characterized in that the tanning of the tannin extract is carried out by reducing pH to 3.5-4.0 after 3.5-7.5 h of permeation at pH 5.0-6.5, and combining for 0.5-1 h at 32-38 ℃.

6. The high temperature dyeable ecological fur chrome-free combination main tanning process of claim 1, wherein said tannin extract is a light-colored tannin extract, including but not limited to any one or more of tara tannin extract, light-colored castanea tannin extract, light-colored wattle bark tannin extract and light-colored quebracho tannin extract.

7. The high temperature dyeable ecological fur chrome-free combination main tanning process of claim 1, wherein said pickle-softened fur comprises, but is not limited to, any one of a sheep fur, a lamb fur, a toscama fur and a beach fur which have been subjected to pickle softening.

8. The chrome-free combined main tanning process of ecological fur which can be dyed at high temperature as claimed in claim 1, characterized in that, before the TWLZ tanning agent is tanned, the process further comprises the steps of adding a nonionic degreasing agent and a grease dispersing agent into the pickling softened fur, and rotating or rowing the leather for 20-40 min at 30-35 ℃;

preferably, the addition amount of the nonionic degreasing agent is 0.5-2 g/L and the addition amount of the grease dispersant is 0.5-3 g/L based on the volume of water added for tanning the fur.

9. The high temperature dyeable ecological fur chrome-free combination main tanning process of claim 3, wherein the solution is alkali stripped with an alkali stripping agent including but not limited to any one or more of sodium bicarbonate, sodium carbonate, magnesium oxide and an autoalkali stripping agent.

10. An ecological fur coat dyeable at high temperature obtained by a chrome-free combined main tanning process as claimed in any one of claims 1 to 9.