CN114410854A

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

Info

Publication number: CN114410854A
Application number: CN202210171254.4A
Authority: CN
Inventors: 余跃; 王亚楠; 石碧; 周建飞; 曾运航; 张文华
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2022-02-24
Filing date: 2022-02-24
Publication date: 2022-04-29

Abstract

The invention belongs to the technical field of leather processing, and discloses a chromium-free combined main tanning process for ecological fur capable of dyeing at high temperature, which is characterized by adopting a combined main tanning process system of TWLZ and plant tanning agent. The excellent dispersion and fixation of the TWLZ tanning agent on the collagen fiber ensures that the plant tanning agent can also uniformly permeate into the leather plate under the conditions of small dosage, high liquor ratio and weak mechanical action, is combined with the TWLZ tanning agent and forms a macromolecular cross-linked network structure in the leather collagen fiber, thereby generating the synergistic tanning effect and endowing the tanned fur with enough wet and hot stability to meet the high-temperature dyeing requirement. The method does not need to use the chromium retanning which is necessary before the original high-temperature dyeing, effectively avoids the generation of chromium-containing wastewater, and is beneficial to promoting the green development of the leather industry.

Description

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

Technical Field

The invention relates to the technical field of leather processing, in particular to a chromium-free combined main tanning process for ecological fur capable of dyeing at high temperature.

Background

Dyeing is one of the important processes for processing fur. By dyeing, the design and color variety of the fur can be increased, and the added value of the finished product is improved. However, the fur quilt has a layer of dense scale layer on the surface, and can be fully opened at high temperature, so that the dye can enter the fur fiber to finish dyeing. Therefore, the fur quilt dyeing needs to be carried out under high temperature conditions.

At present, before fur dyeing, chrome retanning is generally needed to improve the damp-heat stability of the fur, so that the fur meets the high-temperature dyeing requirement. However, the chrome tanning-based process technology inevitably produces a large amount of chromium-containing wastewater. The national standard stipulates that the total chromium emission limit value of a wastewater discharge port of a workshop or a production facility is 1.5 mg/L, and in order to meet the requirement, the wastewater treatment difficulty is high and the cost is high. Therefore, the development of the ecological fur non-chromium tanning process capable of dyeing at high temperature has important significance for improving the sustainability of the fur industry.

The chrome-free tanning technology mainly comprises a non-chrome metal tanning technology and an organic tanning technology. The non-chromium metal tanning agent has a certain tanning effect, but the cross-linking effect on collagen fibers is far inferior to that of a chromium tanning agent, so that the shrinkage temperature of the tanned fur is lower, the skin plate shrinks seriously under the condition of high-temperature dyeing, and the finally obtained dyed fur is in a rigid state and has no use value. The vegetable tanning technology is a typical organic tanning technology, and the tanning extract used by the vegetable tanning technology has the advantages of wide source, reproducibility, no free formaldehyde and the like, and is an environment-friendly tanning agent. However, tannin extracts easily form an aggregated structure in aqueous solution, and are difficult to uniformly permeate into the leather plate under a fur tanning process system with large liquor ratio and weak mechanical action. In addition, the cross-linking effect of tannin extract on collagen fiber is also weak, so that the vegetable-tanned fur is not resistant to high temperature and is difficult to meet the high-temperature dyeing requirement. It follows that a single tanning agent is difficult to impart sufficient wet heat stability to the fur to enable it to meet the high temperature dyeing requirements.

In view of this, the invention is particularly proposed.

Disclosure of Invention

Aiming at the defects of low shrinkage temperature and weak high-temperature tolerance of the tanned fur commonly existing in the prior non-chromium tanning technology, the invention aims to provide a non-chromium combination tanning process of an ecological fur capable of high-temperature dyeing, which is characterized in that the shrinkage temperature of the tanned fur is high, the leather yield is high after high-temperature dyeing, and a leather plate is soft.

In order to achieve the purpose, the invention adopts the technical scheme that:

the ecological fur non-chromium combined main tanning process capable of high temperature dyeing uses pickling softened fur as material and includes tanning with TWLZ tanning agent and tanning with tanning extract.

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

Preferably, the TWLZ tanning agent is used for tanning after the TWLZ tanning agent is infiltrated for 3.5 to 9 hours, alkali is extracted to pH 3.5 to 4.0, and the TWLZ tanning agent is combined for 1 to 4 hours at the temperature of 35 to 42 ℃.

Preferably, the addition amount of the tannin extract is 8-20 g/L calculated by the volume of water added for tanning the fur.

Preferably, the tanning of the tannin extract is performed 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 ℃.

Preferably, the tannin extract is a light-color tannin extract, including but not limited to any one or more of a tara tannin extract, a light-color castanea tannin extract, a light-color wattle tannin extract and a light-color quebracho tannin extract.

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

Preferably, before the TWLZ tanning agent is used for tanning, the method also comprises the steps of adding a nonionic degreasing agent and a grease dispersing agent into the pickled and softened fur, and rotating or scratching for 20-40 min at the temperature of 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.

Preferably, the solution is subjected to alkali extraction using an alkali extracting agent, including, but not limited to, any one or more of sodium bicarbonate, sodium carbonate, magnesium oxide, and an auto-alkali extracting agent.

The invention also provides an ecological fur coat which can be dyed at high temperature and is obtained by adopting any one of the chromium-free combined main tanning processes.

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

(1) the TWLZ tanning agent has excellent dispersing and fixing effects on collagen fibers, so that tanning extract can uniformly permeate into a leather plate under the conditions of high liquid ratio and weak mechanical action, which is a technical effect which is difficult to achieve by the existing fur tanning technology.

(2) According to the invention, the TWLZ and the tannin extract can form a macromolecular cross-linked network structure in the leather collagen fiber, so that the cross-linking effect of the tanning agent on the collagen fiber is obviously improved, and the synergistic tanning effect is generated.

(3) Compared with the existing chrome-free tanning system, the 'TWLZ + tannin extract' combined tanning system provided by the invention can obtain a tanned fur with high shrinkage temperature and strong high-temperature tolerance capacity only through the main tanning process, can meet the requirement of chrome-free high-temperature dyeing, has high leather yield and soft leather plate, does not need chrome retanning, and effectively avoids the generation of chrome-containing wastewater.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The implementation mode provided by the invention is as follows: the ecological fur non-chromium combined main tanning process capable of high temperature dyeing uses pickling softened fur as material and includes tanning with TWLZ tanning agent and tanning with tanning extract.

The existing non-chromium metal tanning agent and tanning fur with tannin extract have the defects of low shrinkage temperature and weak high-temperature tolerance capability, and are difficult to meet the requirements of ecological fur on chromium-free high-temperature dyeing. The applicant finds in experiments that the combined tanning technology of TWLZ and tannin extract can remarkably improve the wet and hot stability of tanned fur, so that the tanned fur can meet the requirement of high-temperature dyeing, and the principle is as follows: the TWLZ tanning agent is a chromium-free complex tanning agent formed by coordination of modified polysaccharide and aluminum-zirconium salt, has better tanning property than conventional aluminum-zirconium salt, and shows excellent dispersion and fixation effects on collagen fibers, so that tanning extract can uniformly permeate into a leather plate, not only can form multi-point hydrogen bond combination with leather collagen, but also can form coordination combination with metal ions in TWLZ, thereby forming a macromolecular cross-linked network structure in a leather collagen fiber network, remarkably improving the cross-linking effect of the tanning agent on the collagen fibers and generating a synergistic tanning effect, leading tanned fur not to shrink the plate under a high-temperature dyeing condition, and finally realizing the chromium-free high-temperature dyeing effect.

In some preferred embodiments, the macerated fur comprises, but is not limited to, any of macerated sheep fur, lamb fur, toscama fur, and beach fur.

In some embodiments, the TWLZ tanning agent is added in an amount of 10-30 g/L based on the volume of water added to tanned fur, i.e., the amount of TWLZ tanning agent added per 1L of water added to tanned fur is 10-30 g, and the TWLZ tanning agent in this concentration range can achieve the invention.

The TWLZ tanning is implemented by permeating the TWLZ tanning agent in a pickling and softening fur for 3.5-9 h, then extracting alkali to pH 3.5-4.0, and combining for 1-4 h at 35-42 ℃.

In order to remove the grease in the pickling softening fur, a step of adding a nonionic degreasing agent and a grease dispersing agent into the pickling softening fur can be further included before adding the TWLZ tanning agent. In some preferred embodiments, the addition amount of the nonionic degreasing agent is 0.5-2 g/L and the addition amount of the grease separating agent is 0.5-3 g/L based on the volume of water added for tanning the fur.

In some specific embodiments, the TWLZ tanning process may be: putting the acid-soaked softened fur obtained by the conventional process into a rotary drum or a scratch groove, adding water with the liquid ratio of 5-20, 50-80 g/L sodium chloride, 0.5-2 g/L nonionic degreasing agent and 0.5-3 g/L grease dispersing agent, controlling the temperature at 30-35 ℃, rotating or scratching for 20-40 min, adding 10-30 g/L TWLZ tanning agent, rotating or scratching for 2-4 h, stopping for 0-1 h, rotating or scratching for 1-2 h, stopping for 0-1 h, repeating the operation of rotating or scratching for 5 min for 8 times every hour, extracting alkali by using an alkali extraction agent until the pH is 3.5-4.0, heating to 35-42 ℃, rotating or scratching for 1-3 h, stopping for 0-1 h, and draining.

Wherein, the tanning liquid is subjected to alkali extraction by using an alkali extraction agent, and the alkali extraction agent comprises any one or more of sodium bicarbonate, sodium carbonate, magnesium oxide and an automatic alkali extraction agent.

The addition amount of the tannin extract is 8-20 g/L calculated by the volume of water added into the tanned fur, namely, the addition amount of the tannin extract is 8-20 g when 1L of water is added into the tanned fur, and the invention can be realized by the tannin extract within the concentration range.

The tanning of the tannin extract is to perform the tanning process on the pickling softened fur tanned by the TWLZ tanning agent after penetrating for 3.5 to 7.5 hours at the pH value of 5.0 to 6.5, reducing the pH value to 3.5 to 4.0 and combining for 0.5 to 1 hour at the temperature of 32 to 38 ℃.

It should be noted that the agents for adjusting the pH of the solution are all conventional in the art, and all agents capable of adjusting the pH of the solution to a target value are intended to fall within the scope of the present invention.

In some preferred embodiments, in order not to affect the colour of the tanned fur, the tannin extract is preferably a light-coloured tannin extract, including but not limited to any one or more of a tara tannin extract, a light-coloured castanea tannin extract, a light-coloured wattle tannin extract and a light-coloured quebracho tannin extract.

In order to further remove grease in the TWLZ tanned fur, a step of adding a grease dispersing agent into the pickling softened fur after being tanned by the TWLZ tanning agent for reaction can be further included before the tannin extract is added. In some preferred embodiments, the oil and fat component is added in an amount of 0.5 to 2 g/L based on the volume of water added to tanned fur.

As in some embodiments, the tanning of the tannin extract may be by: adding water with liquid ratio of 5-20, oil dispersant 0.5-2 g/L and sodium formate 1-3 g/L into the rotary drum or the paddle tank, controlling bath liquid temperature at 35-42 deg.C, increasing bath liquid pH to 5.0-6.0 with sodium bicarbonate, rotating or stroking for 1-2 hr, and draining; adding water with the liquid ratio of 5-20, controlling the bath temperature at 32-38 ℃, adding 2-5 g/L sulfated fatting agent and 8-20 g/L tannin extract, rotating or paddling for 2-4 h, stopping for 0-1 h, rotating or paddling for 1-2 h, repeating the operation of rotating or paddling for 10 min every hour for 3 times, adjusting the pH of the bath to 3.5-4.0 by formic acid, rotating or paddling for 0.5-1 h, and peeling to obtain the ecological chrome-free tanned fur capable of being dyed at high temperature.

In order to better understand the technical scheme provided by the invention, the following specific examples respectively illustrate the eco-leather chrome-free combination main tanning process and the performance test provided by applying the above embodiments of the invention.

In the following examples and comparative examples, the measurement method of the shrinkage temperature of a tanned fur was as follows:

the tanned fur and fur quilts are removed by adopting a shaver, and the fur plate is reserved. And (3) measuring the shrinkage temperature of the leather plate by adopting a shrinkage temperature instrument to represent the damp-heat stability of the tanned fur.

In the following examples and comparative examples, the method for measuring the leather yield of the dyed fur comprises the following steps:

and (3) carrying out high-temperature dyeing on the tanned fur according to a conventional dyeing and finishing process to prepare the dyed fur. A square area board (1 cm) is adopted²/grid) the areas of tanned and dyed furs were measured separately. The calculation formula (1) of the leather yield of the dyed fur is shown. The larger the leather yield is, the smaller the area shrinkage in the high-temperature dyeing process is, and the stronger the temperature resistance of the tanned fur is.

（1）

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

and removing the dyed fur quilt by adopting a shaver, and keeping a leather plate. And (4) determining the softness of the leather plate by using a softness meter.

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

non-ionic degreasing agent: FG-B produced by Sichuan Dawei science and technology Co., Ltd, DW produced by Sichuan Deshel New Material science and technology Co., Ltd, TJ-A124 and TJ-A136 produced by Sichuan Tingjiang New Material Co., Ltd;

grease dispersant: SAF manufactured by derry leather technology (Qingdao) ltd;

TWLZ tanning agent: sichuan Tingjiang New materials Co., Ltd;

automatic alkali extracting agent: MGO produced by Santa Claus Fine paint (Suzhou), MO produced by Sichuan Texel New Material science and technology Co., Ltd, and TJ-A511 produced by Sichuan Tenjiang New Material Co., Ltd;

sulfation fatliquor: kurtalin ABM, Sintoil 88 and Sintoil CH, manufactured by Shihua Italy;

tara tannin extract: TJ-R231, produced by Sichuan Tenjiang New materials GmbH;

light-color castanea mollissima tannin extract: dulcotan specialty, manufactured by Schwara, Italy;

light-colored wattle bark tannin extract: supersol Light manufactured by Brazilian Seta company;

light-colored quebracho tannin extract: indusol Atd, manufactured by Shiwa, Italy.

Example 1

The non-chrome combined main tanning technology of the ecological fur capable of dyeing at high temperature comprises the following steps:

(1) putting the pickling softened sheep fur obtained by the conventional process into a rotary drum, adding water with the liquid ratio of 5, 50 g/L sodium chloride, 1.2 g/L non-ionic degreasing agent FG-B and 1.8 g/L grease dispersing agent SAF, controlling the temperature at 30 ℃, after rotating for 40 min, adding 20 g/L TWLZ tanning agent, rotating for 4 h, stopping rotating for 1 h, stopping for 0.5 h, repeating the operation of rotating for 5 min every hour for 8 times, extracting alkali by magnesium oxide until the pH is 3.5, heating to 35 ℃, rotating for 2 h, stopping for 1 h, draining;

(2) adding water with a liquid ratio of 13, a grease dispersant SAF of 0.5 g/L and sodium formate of 2 g/L into the rotary drum, controlling the temperature of the bath liquid to be 42 ℃, increasing the pH value of the bath liquid to 5.5 by using baking soda, rotating for 1.5 h, and discharging liquid; adding water with the liquid ratio of 5, controlling the temperature of bath liquid to be 38 ℃, adding 3.5 g/L sulfated fatliquor Kurtalin ABM and 14 g/L Light-color wattle bark tannin extract Supersol Light, rotating for 4 h, stopping for 1 h, rotating for 1.5 h, repeating the operation of rotating for 3 times of 10 min per hour, adjusting the pH of the bath liquid to be 3.8 by formic acid, rotating for 0.5 h, and peeling to obtain the ecological chrome-free tanned fur capable of dyeing at high temperature.

The test result shows that the shrinkage temperature of the tanned fur is 103.2 ℃, the leather yield of the fur after high-temperature dyeing is 99.2%, the softness is 7.2 mm, and the test result is shown in table 1.

Comparative example 1

Comparative example 1 differs from example 1 in that comparative example 1 only tanned with 20 g/L of TWLZ tanning agent and no tanning with tanning extract, the detailed process steps being:

putting the pickling softened sheep fur obtained by the conventional process into a rotary drum, adding water with the liquid ratio of 5, 50 g/L sodium chloride, 1.2 g/L non-ionic degreasing agent FG-B and 1.8 g/L grease dispersing agent SAF, controlling the temperature at 30 ℃, after rotating for 40 min, adding 20 g/L TWLZ tanning agent, rotating for 4 h, stopping for 1 h, rotating for 1 h and stopping for 0.5 h, then repeating the operation of rotating for 5 min every hour for 8 times, extracting alkali by magnesium oxide until the pH value is 3.5, heating to 35 ℃, rotating for 2 h, stopping for 1 h, and discharging the tanned fur to obtain the chrome-free fur.

The test result shows that the shrinkage temperature of the tanned fur is 81.4 ℃, the leather yield of the fur after high-temperature dyeing is 73.2%, the softness is 4.3 mm, and the test result is shown in table 1.

Comparative example 2

Comparative example 2 differs from example 1 in that comparative example 2 only tanned with 34 g/L of TWLZ tanning agent and no tanning with tanning extract, the detailed process steps being:

putting the pickling softened sheep fur obtained by the conventional process into a rotary drum, adding water with the liquid ratio of 5, 50 g/L sodium chloride, 1.2 g/L non-ionic degreasing agent FG-B and 1.8 g/L grease dispersing agent SAF, controlling the temperature at 30 ℃, after rotating for 40 min, adding 34 g/L TWLZ tanning agent, rotating for 4 h, stopping for 1 h, rotating for 1 h and stopping for 0.5 h, then repeating the operation of rotating for 5 min every hour for 8 times, extracting alkali by magnesium oxide until the pH value is 3.5, heating to 35 ℃, rotating for 2 h, stopping for 1 h, and discharging the tanned fur to obtain the chrome-free fur.

The test result shows that the shrinkage temperature of the tanned fur is 85.8 ℃, the leather yield of the fur after high-temperature dyeing is 74.3%, the softness is 4.5 mm, and the test result is shown in table 1.

Comparative example 3

Comparative example 3 differs from example 1 in that comparative example 3 only uses a tannin extract of 14 g/L for tanning and does not use a TWLZ tanning agent for tanning, the detailed process steps being:

placing the pickling softened sheep fur obtained by the conventional process in a rotary drum, adding water with a liquid ratio of 13, a fat dispersant SAF of 0.5 g/L and sodium formate of 2 g/L, controlling the bath liquid temperature at 42 ℃, increasing the pH of the bath liquid to 5.5 by using baking soda, rotating for 1.5 h, and discharging liquid; adding water with a liquid ratio of 5, controlling the temperature of bath liquid to be 38 ℃, adding 3.5 g/L sulfated fatliquor Kurtalin ABM and 14 g/L Light-color wattle bark tannin extract Supersol Light, rotating for 4 h, stopping for 1 h, rotating for 1.5 h, repeating the operation of rotating for 3 times of 10 min per hour, adjusting the pH of the bath liquid to be 3.8 by formic acid, rotating for 0.5 h, and peeling to obtain the chrome-free tanned fur.

The test result shows that the shrinkage temperature of the tanned fur is 73.4 ℃, the leather yield of the fur after high-temperature dyeing is 68.5%, the softness is 4.1 mm, and the test result is shown in table 1.

Comparative example 4

Comparative example 4 differs from example 1 in that comparative example 2 only uses a tannin extract of 34 g/L for tanning and does not use a TWLZ tanning agent for tanning, the detailed process steps being:

The test result shows that the shrinkage temperature of the tanned fur is 77.3 ℃, the leather yield of the fur after high-temperature dyeing is 72.3%, the softness is 4.2 mm, and the test result is shown in table 1.

Comparative example 5

Comparative example 5 is different from example 1 in that comparative example 5 replaces the TWLZ tanning agent with a conventional aluminum-zirconium tanning agent in equal amounts and the rest of the procedure is exactly the same as example 1. Comparative example 5 the detailed process steps were:

(1) putting the pickling softened sheep fur obtained by the conventional process into a rotary drum, adding water with the liquid ratio of 5, 50 g/L sodium chloride, 1.2 g/L non-ionic degreasing agent FG-B and 1.8 g/L grease dispersing agent SAF, controlling the temperature at 30 ℃, after rotating for 40 min, adding 20 g/L aluminum-zirconium tanning agent, rotating for 4 h, stopping rotating for 1 h, stopping for 0.5 h, repeating the operation of rotating for 5 min every hour for 8 times, extracting alkali by magnesium oxide until the pH is 3.5, heating to 35 ℃, rotating for 2 h, stopping for 1 h, and discharging liquid;

The test result shows that the shrinkage temperature of the tanned fur is 92.0 ℃, the leather yield of the fur after high-temperature dyeing is 90.7%, the softness is 6.1 mm, and the test result is shown in table 1.

Comparative example 6

Comparative example 6 differs from example 1 in that comparative example 6 replaces the tannin extract with an equal quantity of syntan, the rest of the operation being exactly the same as example 1. Comparative example 6 the detailed process steps were:

(2) adding water with a liquid ratio of 13, a grease dispersant SAF of 0.5 g/L and sodium formate of 2 g/L into the rotary drum, controlling the temperature of the bath liquid to be 42 ℃, increasing the pH value of the bath liquid to 5.5 by using baking soda, rotating for 1.5 h, and discharging liquid; adding water with the liquid ratio of 5, controlling the temperature of bath liquid to be 38 ℃, adding 3.5 g/L sulfated fatting agent Kurtalin ABM and 14 g/L synthetic tanning agent, rotating for 4 h, stopping for 1 h, rotating for 1.5 h, repeating the operation of rotating for 10 min per hour for 3 times, adjusting the pH value of the bath liquid to 3.8 by formic acid, rotating for 0.5 h, and peeling to obtain the ecological chrome-free tanned fur capable of dyeing at high temperature.

The test result shows that the shrinkage temperature of the tanned fur is 90.8 ℃, the leather yield of the fur after high-temperature dyeing is 90.2%, the softness is 5.9 mm, and the test result is shown in table 1.

Comparative example 7

Comparative example 7 differs from example 1 in that comparative example 7 replaces the tannin extract with twice the amount of syntan and the rest of the operation is exactly the same as example 1. Comparative example 7 the detailed process steps were:

(2) adding water with a liquid ratio of 13, a grease dispersant SAF of 0.5 g/L and sodium formate of 2 g/L into the rotary drum, controlling the temperature of the bath liquid to be 42 ℃, increasing the pH value of the bath liquid to 5.5 by using baking soda, rotating for 1.5 h, and discharging liquid; adding water with the liquid ratio of 5, controlling the temperature of bath liquid to be 38 ℃, adding 3.5 g/L sulfated fatting agent Kurtalin ABM and 28 g/L synthetic tanning agent, rotating for 4 h, stopping for 1 h, rotating for 1.5 h, repeating the operation of rotating for 10 min per hour for 3 times, adjusting the pH value of the bath liquid to 3.8 by formic acid, rotating for 0.5 h, and peeling to obtain the ecological chrome-free tanned fur capable of dyeing at high temperature.

The test result shows that the shrinkage temperature of the tanned fur is 95.9 ℃, the leather yield of the fur after high-temperature dyeing is 92.1%, the softness is 6.4 mm, and the test result is shown in table 1.

According to the test results of the example 1 and the comparative examples 1 to 7, the TWLZ and the tannin extract are adopted for combined tanning in the example 1, the shrinkage temperature of the tanned fur is as high as 103.2 ℃, almost no shrinkage is caused after high-temperature dyeing, the leather yield is 99.2%, the dyed fur also keeps good sensory property, and the softness is as high as 7.2 mm; comparative example 1 adopts 20 g/L TWLZ to tanne, the shrinkage temperature of the tanned fur is 81.4 ℃, the leather yield is only 73.2 percent after high-temperature dyeing, the shrinkage plate is obvious, the dyed fur is in a hard plate state, and the softness is only 4.3 mm; comparative example 2 adopts 34 g/L TWLZ to tanne, the shrinkage temperature of the tanned fur is 85.8 ℃, the leather yield is only 74.3 percent after high-temperature dyeing, the shrinkage plate is obvious, the dyed fur is in a hard plate state, and the softness is only 4.5 mm; comparative example 3 tanning with tannin extract of 14 g/L, the shrinkage temperature of the tanned fur is 73.4 ℃, the leather yield is only 68.5% after high-temperature dyeing, the shrinkage is also obvious, the dyed fur is in a hard state, and the softness is only 4.1 mm; comparative example 4 tanning with tannin extract of 34 g/L, the shrinkage temperature of the tanned fur is 77.3 ℃, the leather yield is only 72.3% after high-temperature dyeing, the shrinkage is obvious as well, the dyed fur is in a hard state, and the softness is only 4.2 mm; comparative example 5 tanning with conventional aluminum zirconium tanning agent and tanning extract, shrinkage temperature of tanned fur 92.0 ℃, leather yield of 90.7% after high temperature dyeing, and softness of dyed fur 6.1 mm; comparative example 6 adopts equivalent synthetic tanning agent to replace tanning extract and TWLZ to combine and tan, the shrinkage temperature of the tanned fur is 90.8 ℃, the leather yield is 90.2% after high-temperature dyeing, and the softness of the dyed fur is 5.9 mm; comparative example 7 adopts 2 times of synthetic tanning agent to replace tanning extract to be combined with TWLZ for tanning, the shrinkage temperature of the tanned fur is 95.9 ℃, the leather yield is 92.1 percent after high-temperature dyeing, and the softness of the dyed fur is 6.4 mm.

The shrinkage temperature of the pickled and softened sheep fur was 62.6 ℃, and after combined tanning with 20 g/L TWLZ and 14 g/L tannin extract in example 1, the shrinkage temperature of the tanned fur reached 103.2 ℃, indicating that the shrinkage temperature increase (Δ Ts) of "TWLZ + tannin extract" was 40.6 ℃. The 20 g/L TWLZ tanned fur in comparative example 1 had a shrinkage temperature of 81.4 ℃ and a Δ Ts of 18.8 ℃. The shrinkage temperature of the tanning hide of 14 g/L in comparative example 3 is 73.4 ℃ and the Delta Ts is 10.8 ℃. It can be seen that the Δ Ts of "TWLZ + tannin extract" has exceeded the sum of the TWLZ and tannin extract Δ Ts, i.e. 40.6 ℃ > (18.8 ℃ +10.8 ℃), indicating that the "TWLZ + tannin extract" combined tanning process employed in the present invention produces a significant synergistic tanning effect. The TWLZ tanned fur of comparative example 2 at 34 g/L had a shrinkage temperature of 85.8 ℃ and a Δ Ts of 23.2 ℃. The shrinkage temperature of the tannin extract tanned fur in comparative example 4 at 34 g/L was 77.3 ℃ and Δ Ts was 14.7 ℃. Likewise, the Δ Ts of "TWLZ + tannin extract" has exceeded the sum of TWLZ and tannin extract Δ Ts, i.e., 40.6 ℃ > (23.2 ℃ +14.7 ℃), indicating that the "TWLZ + tannin extract" combined tanning process employed in the present invention still produces a significant synergistic tanning effect at the same tanning agent dosage.

The shrinkage temperature and the temperature resistance of the tanned fur in example 1 are all superior to those of comparative example 5, which shows that the conventional aluminum-zirconium tanning agent can not replace the TWLZ tanning agent to obtain the technical effects of high shrinkage temperature and strong temperature resistance which are expected to be realized in the invention. This is mainly due to the fact that the conventional aluminium-zirconium tanning agent does not contain modified polysaccharide ligands, so that the formed complex has a lower dispersion and fixing capacity for collagen fibres than the TWLZ tanning agent, resulting in the difficulty of uniform penetration of the tanning extract. In addition, the shrinkage temperature and temperature resistance of the tanned furs of example 1 are also superior to those of comparative examples 6 and 7, which shows that the technical effect intended to be achieved in the present invention cannot be obtained by replacing tannin extracts even with 2 times the amount of synthetic tanning agent. This is mainly due to the fact that the synthetic tanning agents have small molecular weight and few phenolic hydroxyl groups and are difficult to form macromolecular cross-linked network structures after coordination with TWLZ. The results of the above examples and comparative examples show that the synergistic tanning process of "TWLZ + tannin extract" used according to the invention represents a significant advance over the prior art, producing unexpected results.

TABLE 1 test results

。

Example 2

(1) placing the acid-soaked and softened lamb fur obtained by a conventional process into a scratching groove, adding water with a liquid ratio of 13, 80 g/L sodium chloride, 2 g/L nonionic degreasing agent DW and 0.5 g/L grease dispersing agent SAF, controlling the temperature at 32 ℃, scratching for 30 min, adding 10 g/L TWLZ tanning agent, scratching for 4.5 h, repeating the operation of scratching for 5 min every hour for 8 times, extracting alkali by using sodium bicarbonate until the pH value is 4.0, heating to 42 ℃, scratching for 1 h, and discharging liquid;

(2) adding water with a liquid ratio of 20, a grease dispersant SAF with a liquid ratio of 2 g/L and sodium formate with a liquid ratio of 1 g/L into the groove, controlling the temperature of the bath liquid to be 35 ℃, increasing the pH value of the bath liquid to 5.0 by using sodium bicarbonate, performing rowing for 2 h, and discharging the liquid; adding water with the liquid ratio of 20, controlling the bath temperature to be 32 ℃, adding 2 g/L sulfated fatliquor Sintoil 88 and 20 g/L tara tannin extract TJ-R231, paddling for 5 h, repeating the operation of paddling for 10 min per hour for 3 times, adjusting the pH of the bath to 3.5 by formic acid, paddling for 0.8 h, and peeling to obtain the ecological chrome-free tanned fur capable of dyeing at high temperature.

The test shows that the shrinkage temperature of the tanned fur is 99.7 ℃, the leather yield of the fur after high-temperature dyeing is 98.6%, and the softness is 7.0 mm.

Example 3

(1) putting the acid-soaked softened toscarna sheepskin obtained by the conventional process into a rotary drum, adding water with the liquid ratio of 20, 65 g/L sodium chloride, 0.5 g/L nonionic degreasing agent TJ-A124 and 3 g/L grease dispersing agent SAF, controlling the temperature at 35 ℃, after rotating for 20 min, adding 30 g/L TWLZ tanning agent, rotating for 2 h, stopping for 0.5 h, rotating for 2 h, stopping for 1 h, repeating the operation of rotating for 5 min every hour for 8 times, after alkali is extracted by sodium carbonate until the pH is 3.8, heating to 38 ℃, rotating for 3 h, stopping for 0.5 h, and discharging liquid;

(2) adding water with a liquid ratio of 5, a grease dispersant SAF with a liquid ratio of 1.2 g/L and sodium formate with a liquid ratio of 3 g/L into a rotary drum, controlling the temperature of bath liquid to be 38 ℃, increasing the pH value of the bath liquid to 6.0 by using baking soda, rotating for 1 h, and discharging liquid; adding water with a liquid ratio of 13, controlling the temperature of bath liquid to be 35 ℃, adding 5 g/L sulfated fatting agent Sintoil CH and 8 g/L light-color castanea mollissima extract Dulcotan Special, rotating for 2 h, stopping for 0.5 h, rotating for 1 h, repeating the operation of rotating for 10 min every hour for 3 times, adjusting the pH value of the bath liquid to 4.0 by formic acid, rotating for 1 h, and peeling to obtain the ecological chromium-free tanned fur capable of being dyed at high temperature.

The test shows that the shrinkage temperature of the tanned fur is 105.9 ℃, the leather yield of the fur after high-temperature dyeing is 99.4%, and the softness is 7.4 mm.

Example 4

(1) putting the soaked and softened Tan sheep fur obtained by the conventional process into a scratching groove, adding water with the liquid ratio of 20, 65 g/L sodium chloride, 1.2 g/L nonionic degreasing agent TJ-A126 and 0.5 g/L grease dispersing agent SAF, controlling the temperature at 30 ℃, after scratching for 20 min, adding 30 g/L TWLZ tanning agent, scratching for 4 h, stopping scratching for 0.5 h, scratching for 1 h, repeating the operation of scratching for 5 min every hour for 8 times, extracting alkali by using an automatic alkali extraction agent MGO until the pH value is 3.8, heating to 38 ℃, scratching for 3 h, stopping for 0.5 h, and discharging liquid;

(2) adding water with a liquid ratio of 13, a grease dispersing agent SAF with a liquid ratio of 2 g/L and sodium formate with a liquid ratio of 2 g/L into the paddle vat, controlling the temperature of the bath liquid to be 38 ℃, increasing the pH value of the bath liquid to 5.5 by using baking soda, stroking for 1 h, and discharging liquid; adding water with the liquid ratio of 20, controlling the bath liquid temperature to be 38 ℃, adding 3.5 g/L sulfated fatliquor Kurtalin ABM and 14 g/L light-color quebracho tannin extract Induslo Atd, paddling for 3 hours, repeating the operation of paddling for 10 min per hour for 3 times, regulating the pH value of the bath liquid to be 4.0 by formic acid, paddling for 1 hour, and peeling to obtain the ecological chrome-free tanned fur capable of dyeing at high temperature.

The test shows that the shrinkage temperature of the tanned fur is 107.5 ℃, the leather yield of the fur after high-temperature dyeing is 99.6%, and the softness is 7.5 mm.

Example 5

(1) putting the pickling softened sheep fur obtained by the conventional process into a rotary drum, adding water with a liquid ratio of 13, 80 g/L sodium chloride, 2 g/L non-ionic degreasing agent FG-B and 1.8 g/L grease dispersing agent SAF, controlling the temperature at 35 ℃, rotating for 30 min, adding 10 g/L TWLZ tanning agent, rotating for 4.5 h, stopping for 1 h, repeating the operation of rotating for 5 min every hour for 8 times, extracting alkali by using an automatic alkali-extracting agent MO until the pH value is 4.0, heating to 42 ℃, rotating for 1 h, and discharging liquid;

(2) adding water with a liquid ratio of 5, a grease dispersant SAF with a liquid ratio of 0.5 g/L and sodium formate with a liquid ratio of 1 g/L into a rotary drum, controlling the temperature of bath liquid to be 35 ℃, increasing the pH value of the bath liquid to 5.0 by using baking soda, rotating for 2 hours, and discharging liquid; adding water with the liquid ratio of 5, controlling the bath temperature to be 32 ℃, adding 2 g/L sulfated fatliquor Sintoil 88, 4 g/L tara tannin extract TJ-R231 and 4 g/L light-color chestnut tannin extract Dulcotan Special, rotating for 3 hours, stopping for 0.5 hour, rotating for 2 hours, repeating the operation of rotating for 10 minutes per hour for 3 times, adjusting the pH of the bath solution to 3.5 by formic acid, rotating for 0.5 hour, and discharging to obtain the ecological chrome-free tanned fur capable of being dyed at high temperature.

The test shows that the shrinkage temperature of the tanned fur is 99.2 ℃, the leather yield of the fur after high-temperature dyeing is 98.3%, and the softness is 6.8 mm.

Example 6

(1) placing the acid-soaked softened lamb fur obtained by a conventional process into a scratching groove, adding water with the liquid ratio of 5, 50 g/L sodium chloride, 0.5 g/L nonionic degreasing agent DW and 3 g/L grease dispersing agent SAF, controlling the temperature at 32 ℃, scratching for 40 min, adding 20 g/L TWLZ tanning agent, scratching for 2 h, stopping scratching for 1 h, scratching for 2 h and stopping for 0.5 h, repeating the operation of scratching for 5 min every hour for 8 times, extracting alkali by using an automatic alkali extraction agent TJ-A511 until the pH value is 3.5, heating to 35 ℃, scratching for 2 h, stopping for 1 h, and discharging liquid;

(2) adding water with a liquid ratio of 20, a grease dispersing agent SAF with a concentration of 1.2 g/L and sodium formate with a concentration of 3 g/L into the paddle bath, controlling the bath liquid temperature at 42 ℃, increasing the pH value of the bath liquid to 5.0 by using sodium bicarbonate, stroking for 1 h, and discharging liquid; adding water with the liquid ratio of 20, controlling the bath temperature to be 32 ℃, adding 2 g/L sulfated fatliquor Sintoil CH, 7 g/L Light-color quebracho extract Indusol Atd and 7 g/L Light-color quebracho extract Supersol Light, scratching for 2 h, stopping for 1 h, scratching for 2 h, repeating the operation of scratching for 10 min every hour for 3 times, adjusting the pH of the bath solution to 3.8 by formic acid, scratching for 0.5 h, and peeling to obtain the ecological chrome-free tanned fur capable of being dyed at high temperature.

The test shows that the shrinkage temperature of the tanned fur is 99.4 ℃, the leather yield of the fur after high-temperature dyeing is 98.5%, and the softness is 6.9 mm.

Example 7

(1) putting the acid-soaked softened toscarna sheepskin obtained by the conventional process into a rotary drum, adding water with the liquid ratio of 5, 50 g/L sodium chloride, 2 g/L nonionic degreasing agent TJ-A124 and 1.8 g/L grease dispersing agent SAF, controlling the temperature at 32 ℃, after rotating for 30 min, adding 10 g/L TWLZ tanning agent, rotating for 3 h, stopping for 1 h, rotating for 2 h and stopping for 1 h, repeating the operation of rotating for 5 min every hour for 8 times, extracting alkali by using sodium bicarbonate and magnesium oxide until the pH value is 3.5, heating to 35 ℃, rotating for 1 h, and discharging liquid;

(2) adding water with a liquid ratio of 5, a grease dispersant SAF with a liquid ratio of 1.2 g/L and sodium formate with a liquid ratio of 1 g/L into a rotary drum, controlling the temperature of bath liquid to be 42 ℃, increasing the pH value of the bath liquid to 5.0 by using baking soda, rotating for 1 h, and discharging liquid; adding water with the liquid ratio of 20, controlling the bath temperature to be 32 ℃, adding 2 g/L sulfated fatliquor Kurtalin ABM, 7 g/L tara extract TJ-R231 and 7 g/L Light-color wattle extract Supersol Light, rotating for 2 h, stopping for 1 h, rotating for 2 h, repeating the operation of rotating for 10 min every hour for 3 times, adjusting the pH of the bath solution to 3.8 by formic acid, rotating for 0.5 h, and discharging to obtain the ecological chrome-free tanned fur capable of being dyed at high temperature.

Example 8

(1) putting the soaked and softened Tan sheep fur obtained by the conventional process into a scratching groove, adding water with the liquid ratio of 13, 80 g/L sodium chloride, 0.5 g/L non-ionic degreasing agent TJ-A126 and 0.5 g/L grease dispersing agent SAF, controlling the temperature at 30 ℃, after scratching for 20 min, adding 20 g/L TWLZ tanning agent, scratching for 2 h, stopping scratching for 0.5 h, scratching for 1 h, stopping scratching for 0.5 h, repeating the operation of scratching for 5 min every hour for 8 times, extracting alkali by using sodium carbonate and magnesium oxide until the pH is 3.8, heating to 38 ℃, scratching for 2 h, stopping for 0.5 h, and draining;

(2) adding water with a liquid ratio of 20, a grease dispersant SAF with a liquid ratio of 2 g/L and sodium formate with a liquid ratio of 3 g/L into the groove, controlling the temperature of the bath liquid to be 35 ℃, increasing the pH value of the bath liquid to 6.0 by using sodium bicarbonate, and performing rowing for 1.5 h to discharge liquid; adding water with a liquid ratio of 13, controlling the bath temperature to 35 ℃, adding 3.5 g/L sulfated fatliquor Sintoil 88, 4 g/L Light-color castanea tannin extract Dulcotan Special and 4 g/L Light-color castanea tannin extract Supersol Light, scratching for 3 h, stopping for 0.5 h, scratching for 1 h, repeating the scratching operation for 3 times of 10 min per hour, scratching for 0.8 h after regulating the pH of the bath solution to 3.5 by formic acid, and discharging to obtain the ecological chrome-free tanned fur capable of being dyed at high temperature.

The test shows that the shrinkage temperature of the tanned fur is 101.9 ℃, the leather yield of the fur after high-temperature dyeing is 98.9%, and the softness is 7.1 mm.

Example 9

(1) putting the acid-soaked softened lamb fur obtained by the conventional process into a rotary drum, adding water with the liquid ratio of 20, 65 g/L sodium chloride, 1.2 g/L non-ionic degreasing agent FG-B and 3 g/L grease dispersing agent SAF, controlling the temperature at 35 ℃, rotating for 40 min, adding 30 g/L TWLZ tanning agent, rotating for 5.5 h, repeating the operation of rotating for 5 min every hour for 8 times, extracting alkali by using sodium carbonate and automatic alkali extraction agent TJ-511 until the pH value is 4.0, heating to 42 ℃, rotating for 3 h, stopping for 1 h, and discharging liquid;

(2) adding water with a liquid ratio of 13, a grease dispersant SAF with a liquid ratio of 0.5 g/L and sodium formate with a liquid ratio of 2 g/L into a rotary drum, controlling the temperature of bath liquid to be 38 ℃, increasing the pH value of the bath liquid to 5.5 by using baking soda, rotating for 2 hours, and discharging liquid; adding water with the liquid ratio of 5, controlling the bath temperature to be 38 ℃, adding 5 g/L sulfated fatliquor Sintoil CH, 7 g/L Light-color castanea mollissima extract Dultosan specific, 7 g/L Light-color quebracho extract Indusol Atd and 6 g/L Light-color wattle extract Supersol Light, rotating for 5.5 h, repeating the operation of rotating for 10 min every hour for 3 times, adjusting the pH of the bath solution to 4.0 by formic acid, rotating for 1 h, and discharging to obtain the ecological chrome-free tanned fur capable of being dyed at high temperature.

The test shows that the shrinkage temperature of the tanned fur is 108.4 ℃, the leather yield of the fur after high-temperature dyeing is 99.7%, and the softness is 7.6 mm.

Example 10

(1) putting the pickling softened sheep fur obtained by the conventional process into a scratching groove, adding water with a liquid ratio of 13, 65 g/L sodium chloride, 2 g/L nonionic degreasing agent DW and 3 g/L grease dispersing agent SAF, controlling the temperature at 35 ℃, adding 30 g/L TWLZ tanning agent after scratching for 40 min, scratching for 3 h, stopping scratching for 0.5 h, scratching for 1.5 h and stopping scratching for 0.5 h, repeating the operation of scratching for 5 min every hour for 8 times, extracting alkali by using sodium bicarbonate and an automatic alkali extraction agent MGO until the pH value is 4.0, heating to 38 ℃, scratching for 2 h, stopping for 0.5 h, and discharging liquid;

(2) adding water with a liquid ratio of 13, a grease dispersing agent SAF with a concentration of 1.2 g/L and sodium formate with a concentration of 2 g/L into the paddle bath, controlling the bath liquid temperature to be 38 ℃, increasing the pH value of the bath liquid to 6.0 by using sodium bicarbonate, stroking for 1 h, and discharging liquid; adding water with a liquid ratio of 13, controlling the bath temperature to 35 ℃, adding 5 g/L sulfated fatliquor Sintoil 88, 5 g/L tara extract TJ-R231, 5 g/L Light-color chestnut extract Dulcotan Special, 5 g/L Light-color wattle extract super Light and 5 g/L Light-color quebracho extract Indusol Atd, scratching for 3 h, stopping for 0.5 h, scratching for 1 h, repeating the operation of scratching for 10 min per hour for 3 times, adjusting the pH of the bath to 3.8 by formic acid, scratching for 0.8 h, and peeling to obtain the ecological chrome-free tanned fur capable of being dyed at high temperature.

The test shows that the shrinkage temperature of the tanned fur is 108.6 ℃, the leather yield of the fur after high-temperature dyeing is 99.7%, and the softness is 7.6 mm.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims

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 ℃;

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.