WO2023159773A1 - 生态皮革无铬鞣制工艺 - Google Patents

生态皮革无铬鞣制工艺 Download PDF

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Publication number
WO2023159773A1
WO2023159773A1 PCT/CN2022/092095 CN2022092095W WO2023159773A1 WO 2023159773 A1 WO2023159773 A1 WO 2023159773A1 CN 2022092095 W CN2022092095 W CN 2022092095W WO 2023159773 A1 WO2023159773 A1 WO 2023159773A1
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leather
tanning
chrome
twlz
tws
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PCT/CN2022/092095
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English (en)
French (fr)
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王亚楠
余跃
石碧
周建飞
曾运航
张文华
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四川大学
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Publication of WO2023159773A1 publication Critical patent/WO2023159773A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/04—Mineral tanning
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/24—Chemical tanning by organic agents using lignin derivatives, e.g. sulfate liquor
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/28—Multi-step processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

Definitions

  • the invention belongs to the technical field of leather processing, in particular to a chrome-free tanning process of ecological leather.
  • Chinese patent CN103060488B "A Production Method for Environmentally Friendly Parquet” discloses a method for tanning wet white leather with an organic tanning agent TWS, and fixing it with a chrome tanning agent after dyeing and finishing to prepare an environmentally friendly parison leather.
  • TWS tanning agent mainly reacts with the amino group of skin collagen, makes the isoelectric point of tanned wet white leather not exceed 5.0, causes follow-up dyeing and finishing material (generally anionic at present)
  • the combination rate of dyeing and finishing materials is not high enough, which not only causes waste of dyeing and finishing materials, but also increases the organic pollution load in dyeing and finishing wastewater.
  • the present invention provides a chrome-free tanning process for ecological leather to obtain leather with sufficient and uniform tanning, a high isoelectric point, and good softness.
  • the chrome-free tanning process of ecological leather uses pickled bare leather as raw material, first tans with TWS tanning agent, adds sodium lignosulfonate for reaction, and then uses TWLZ tanning agent for tanning.
  • the TWS tanning agent is added in an amount of 1-5wt% based on the weight of the limed bare hide, the added amount of the sodium lignosulfonate is 1-4wt%, and the added amount of the TWLZ tanning agent is 2-6 wt%.
  • the TWS tanning agent is tanned by infiltrating the TWS tanning agent for 2-4 hours, raising the base to 7.0-8.5, and combining at 35-42° C. for 1-3 hours.
  • the TWLZ tanning agent is infiltrated at pH 3.0-4.5 for 1-4 hours, the base is raised to pH 3.5-4.5, and combined at 35-42°C for 1-4 hours.
  • the pickled bare hide includes but not limited to any one of pickled sheep hide, pickled goat hide and pickled cow hide.
  • an alkali-raising agent is used for alkali-raising, and the alkali-raising agent includes but is not limited to any one or more of sodium bicarbonate, sodium carbonate, magnesium oxide and an automatic alkali-raising agent.
  • the invention also discloses the ecological leather obtained by adopting any one of the chrome-free tanning techniques mentioned above.
  • the present invention has the following beneficial effects:
  • sodium lignosulfonate can assist in fixing the TWS tanning agent, so that TWS tanned leather does not tan under low pH conditions. Detanning will occur, and it can also improve the distribution uniformity of TWLZ tanning agent in the hide, so that the tanning effect of the three-component tanning system is significantly better than that of the existing TWS, TWLZ and "TWS+TWLZ" combined tanning systems.
  • the chrome-free tanning system of ternary ecological leather constructed by the present invention can obtain leather with fully uniform tanning, high isoelectric point, strong electropositive property, good absorption of dyeing and finishing materials and soft leather body, endowing the leather with wider use Range and better quality, this is the effect that the existing technology is difficult to achieve.
  • the embodiment provided by the present invention is the chrome-free tanning process of ecological leather, using pickling bare hide as raw material, first using chrome-free organic tanning agent TWS for tanning, adding sodium lignosulfonate for reaction, and then using chrome-free metal tanning agent TWLZ tanned.
  • TWS tanning agent and TWLZ tanning agent are difficult to obtain leather with sufficient uniform tanning, high isoelectric point and good softness through simple combination.
  • the pH of the solution is usually less than 3.0.
  • the TWS tanned leather will undergo obvious untanning, which will weaken the dispersion and fixation effect of the TWS tanning agent on the fiber, and it will be difficult for the TWLZ tanning agent to penetrate into the leather evenly, eventually leading to tanning.
  • the shrinkage temperature is insufficient, and the softness of the finished leather is not good.
  • the reaction mechanism is: lignosulfonic acid
  • the molecular structure of sodium contains active functional groups such as phenolic hydroxyl group and sulfonic acid group. Its phenolic hydroxyl group can form multi-point hydrogen bonds with TWS tanning agent and skin collagen. At the same time, the hydrophobicity of its benzene ring also forms a fixation effect on TWS tanning agent.
  • TWLZ tanning agent can form a coordination combination with the sulfonic acid group in sodium lignosulfonate to form a stable cross-linked network structure in the skin collagen fibers, and finally obtain leather products with high shrinkage temperature and good softness.
  • the pickled bare hide is the pickled bare hide obtained according to the conventional process in this field.
  • the pickled bare hide includes but not limited to pickled sheep skin, pickled goat skin and any of the pickled cowhide.
  • the added amount of the chrome-free organic tanning agent TWS is 1-5 wt%
  • the added amount of the sodium lignosulfonate is 1-4 wt%
  • the added amount of the chrome-free organic tanning agent TWS is 1-5 wt%.
  • the addition amount of chrome metal tanning agent TWLZ is 2-6wt%.
  • the chrome-free organic tanning agent TWS is used for tanning.
  • the chrome-free organic tanning agent TWS is permeated into the pickled bare hide for 2-4 hours, the alkali is raised to 7.0-8.5, and combined at 35-42°C for 1-3 hours.
  • the pickled hides obtained by the conventional process are placed in a drum, and 30-100wt% of pickling solution and 1-5wt% of chrome-free Organic tanning agent TWS, rotate for 2-4h, after raising the base to a pH of 7.0-8.5, add hot water of 100-200wt% by weight of liming bare hide, keep the temperature of the bath liquid at 35-42°C, and rotate for 1 -3h, stop the drum overnight, and drain the liquid after turning for 0.5h the next day.
  • the chrome-free metal tanning agent TWLZ is infiltrated at pH 3.0-4.5 for 1-4 hours, the base is raised to pH 3.5-4.5, and combined at 35-42°C for 1-4 hours.
  • the pH of the bath solution 3.0-4.5
  • the pH is 3.5-4.5
  • the specific method of adding sodium lignosulfonate to the reaction is to add 30-100wt% normal temperature water and 1-4wt% by weight of liming bare hide to the mixture tanned by the chrome-free organic tanning agent TWS % sodium lignosulfonate, rotate for 0.5-2h.
  • Alkali-enhancing agent is used for alkali-enhancing.
  • the alkali-enhancing agent includes but not limited to any one or more of sodium bicarbonate, sodium carbonate, magnesium oxide and automatic alkali-enhancing agent.
  • the assay method of TWLZ tanning agent distribution uniformity in leather is:
  • TWLZ tanning agent Use a frozen microtome to divide the tanned wet white leather evenly into grain layer, middle layer and flesh layer, dry at 102 ⁇ 2°C until constant weight, then weigh a certain quality of dry skin samples into the digestion tube, Nitric acid and hydrogen peroxide were added, after being digested by a microwave digestion apparatus, the volume was constant, and then the content of metal ions in each layer of samples was measured by an inductively coupled plasma generation spectrometer.
  • the formula for calculating the distribution uniformity of TWLZ tanning agent in wet white leather is as follows:
  • the measuring method of the isoelectric point of tanned wet white leather is:
  • the assay method of the shrinkage temperature of tanned wet white leather is:
  • the shrinkage temperature of wet white leather was measured with a shrinkage thermometer.
  • the assay method of leather crust softness is:
  • the tanned wet white leather was dyed and finished according to the conventional process to obtain crust leather, and the softness of the crust leather was measured by a softness tester.
  • Comparative Example 1 only uses 5wt% TWS tanning agent for tanning, and does not use sodium lignosulfonate and TWLZ tanning agent for tanning.
  • the detailed process steps are:
  • Example 2 has adopted 9wt% TWS tanning agent for tanning, but not sodium lignosulfonate and TWLZ tanning agent for tanning, and the detailed process steps are:
  • Comparative Example 3 only uses 4wt% TWLZ tanning agent for tanning, and does not use TWS tanning agent and sodium lignosulfonate for tanning.
  • the detailed process steps are:
  • the pickled cowhide obtained by the conventional process in the drum add 60wt% pickling solution based on the weight of the limed bare hide and 4wt% chrome-free metal tanning agent TWLZ, rotate for 4 hours, and use the automatic alkali-raising agent MGO Elevate alkali to pH 4.0, add 200wt% hot water by weight of liming bare skin, keep the temperature of bath liquid at 38°C, rotate for 4 hours, stop the drum overnight, turn it for 0.5 hour the next day, and take out the drum to obtain tanned white wet leather.
  • Example 4 has adopted the TWLZ tanning agent of 9wt% to carry out tanning, has not adopted TWS tanning agent and sodium lignosulfonate to carry out tanning, and detailed process step is:
  • the pickled cowhide obtained according to the conventional process in the drum add 60wt% pickling solution based on the weight of the limed bare hide and 9wt% chrome-free metal tanning agent TWLZ, rotate for 4 hours, and use the automatic alkali-raising agent MGO Elevate alkali to pH 4.0, add 200wt% hot water by weight of liming bare skin, keep the temperature of bath liquid at 38°C, rotate for 4 hours, stop the drum overnight, turn it for 0.5 hour the next day, and take out the drum to obtain tanned white wet leather.
  • Example 5 uses the "TWS+TWLZ" combination for tanning, it does not use sodium lignosulfonate for tanning.
  • the detailed process steps are:
  • Comparative Example 1 uses 4wt% TWS tanning agent for tanning, the isoelectric point of wet white leather is only 4.9, the shrinkage temperature is 84.5°C, and the crust leather is soft The thickness is 7.0mm;
  • comparative example 2 uses 9wt% TWS tanning agent for tanning, the isoelectric point of wet white leather is only 5.0, the shrinkage temperature is 85.6 °C, and the softness of crust leather is 7.1mm;
  • comparative example 3 adopts 5wt% TWS tanning agent Tanning with TWLZ tanning agent, TWLZ distribution uniformity is 92.7%, the isoelectric point of wet white leather is 7.2, the shrinkage temperature is only 69.2°C, and the softness of crust leather is as low as 5.4mm;
  • comparative example 4 adopts 9wt% TWLZ tanning agent for tanning Tanning, the TWLZ distribution uniformity is 93.2%, the isoelectric point of wet white
  • the shrinkage temperature of the tanned leather and the softness of the leather are lower; while the combination of "TWS+sodium lignosulfonate+TWLZ" is used for tanning leather, due to the hydrophobic effect of sodium lignosulfonate through its benzene ring and the multiple formation of its hydroxyl group
  • the point hydrogen bond structure forms a fixed effect on the TWS tanning agent, making the collagen fibers in a dispersed state, so the distribution uniformity of TWLZ is significantly improved, the isoelectric point and shrinkage temperature of wet white leather are higher, and the softness even exceeds that of TWS alone Tanned crust leather.
  • TWLZ tanning agent in wet white leather is 98.5%
  • the isoelectric point of wet white leather is 7.5
  • the shrinkage temperature of wet white leather is 96.9°C
  • the softness of leather after dyeing and finishing is 8.4mm .
  • TWLZ tanning agent in wet white leather is 98.8%
  • the isoelectric point of wet white leather is 6.7
  • the shrinkage temperature of wet white leather is 90.4°C
  • the softness of leather after dyeing and finishing is 7.8mm .
  • TWLZ tanning agent in wet white leather is 97.9%, the isoelectric point of wet white leather is 7.4, the shrinkage temperature of wet white leather is 91.3°C, and the softness of leather after dyeing and finishing is 7.6mm .
  • TWLZ tanning agent in wet white leather is 99.1%
  • the isoelectric point of wet white leather is 7.0
  • the shrinkage temperature of wet white leather is 98.8°C
  • the softness of leather after dyeing and finishing is 8.7mm .
  • TWLZ tanning agent in wet white leather is 98.4%
  • the isoelectric point of wet white leather is 6.6
  • the shrinkage temperature of wet white leather is 95.4°C
  • the softness of leather after dyeing and finishing is 8.2mm .
  • TWLZ tanning agent in wet white leather is 97.6%
  • the isoelectric point of wet white leather is 6.5
  • the shrinkage temperature of wet white leather is 90.8°C
  • the softness of leather after dyeing and finishing is 7.4mm .
  • TWLZ tanning agent in wet white leather is 99.4%
  • the isoelectric point of wet white leather is 7.5
  • the shrinkage temperature of wet white leather is 100.2°C
  • the softness of leather after dyeing and finishing is 8.8mm .
  • TWLZ tanning agent in wet white leather is 98.3%
  • the isoelectric point of wet white leather is 7.0
  • the shrinkage temperature of wet white leather is 94.1°C
  • the softness of leather after dyeing and finishing is 7.9mm .
  • TWLZ tanning agent in wet white leather is 99.0%
  • the isoelectric point of wet white leather is 7.3
  • the shrinkage temperature of wet white leather is 93.7°C
  • the softness of leather after dyeing and finishing is 7.9mm .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

本发明属于皮革加工技术领域，公开了生态皮革无铬鞣制工艺，其特点是采用了"TWS+木质素磺酸钠+TWLZ"三元鞣制工艺体系。木质素磺酸钠的加入不仅对TWS鞣剂形成了固定作用，使得TWS鞣革在低pH条件下不会发生退鞣，而且还能显著提升TWLZ鞣剂在皮中的分布均匀性并促使TWLZ鞣剂在皮胶原纤维中形成稳定的交联网络结构，有效克服了现有鞣制体系鞣革性能的缺陷，获得鞣制均匀充分、等电点高、阳电性强、对染整材料吸收好且革身柔软的皮革，赋予皮革更宽的使用范围和更优的品质。

Description

生态皮革无铬鞣制工艺 技术领域
本发明属于皮革加工技术领域，特别涉及生态皮革无铬鞣制工艺。
背景技术
生态皮革制造，是全球皮革行业最重要的战略目标。铬鞣法因其能赋予皮革极优的湿热稳定性和成革综合性能而成为当前皮革行业占据主导地位的鞣制方法。但是，铬鞣会产生含铬废水和固废等问题，具有潜在的环境风险。因此，开发新的生态皮革无铬鞣制技术，从源头消除铬污染，是皮革行业可持续发展亟待解决的关键科技问题。
中国专利CN103060488B“一种环保型坯革生产方法”公开了一种采用有机鞣剂TWS鞣制白湿革，经染整后用铬鞣剂固定来制备环保型坯革的方法。该方法制得的坯革柔软度好，但存在的问题是TWS鞣剂主要与皮胶原的氨基反应，使得鞣制白湿革的等电点不超过5.0，导致后续染整材料(目前普遍为阴离子型材料)的结合率不够高，不仅造成染整材料的浪费，而且还会增加染整废水中的有机污染负荷。中国专利CN110628968B“绵羊皮革无铬鞣的加工工艺及绵羊白湿皮与绵羊皮革”公开了一种采用无铬金属鞣剂TWLZ鞣制白湿革的方法。该方法中TWLZ鞣剂呈阳电性，且主要与皮胶原的羧基发生配位反应，使得白湿革的等电点达到7.0以上，对阴离子染整材料具有良好的吸收和结合能力，但存在的问题是白湿革经染整后制得的坯革柔软度较低，难于满足当今皮革产品对于“软、泡”的要求。由于存在上述问题，TWS和TWLZ无铬鞣制技术的推广应用受到一定限制。
鉴于此，特提出本发明。
发明内容
为解决背景技术中的问题，本发明的在于提供生态皮革无铬鞣制工艺，获得鞣制充分均匀、等电点高、柔软度好的皮革。
为达到上述目的，本发明采用的技术方案为：
生态皮革无铬鞣制工艺，以浸酸裸皮为原料，先使用TWS鞣剂鞣制，加入木质素磺酸钠反应后，再使用TWLZ鞣剂鞣制。
优选的，以浸灰裸皮重量计，所述TWS鞣剂的添加量为1-5wt％，所述木质素磺酸钠的添加量为1-4wt％，所述TWLZ鞣剂的添加量为2-6wt％。
优选的，所述TWS鞣剂进行鞣制是将TWS鞣剂渗透2-4h，提碱至7.0-8.5，35-42℃下结合1-3h。
优选的，所述TWLZ鞣剂是在pH 3.0-4.5渗透1-4h，提碱至pH 3.5-4.5，35-42℃下结合1-4h。
优选的，加入木质素磺酸钠在常温下反应0.5-2h。
优选的，所述浸酸裸皮包含但不限于浸酸绵羊皮、浸酸山羊皮和浸酸牛皮中任一种。
优选的，采用提碱剂进行提碱，所述提碱剂包含但不限于碳酸氢钠、碳酸钠、氧化镁和自动提碱剂中任一种或多种。
本发明还公开了采用上述任一所述无铬鞣制工艺得到的生态皮革。
本发明与现有技术相比，具有以下有益效果：
(1)本发明构建的“TWS+木质素磺酸钠+TWLZ”三元生态皮革无铬鞣制体系中，木质素磺酸钠既能协助固定TWS鞣剂，使得TWS鞣革在低pH条件下不会发生退鞣，亦能提升TWLZ鞣剂在皮中的分布均匀性，使得三元鞣制体系的鞣制效果显著优于现有TWS、TWLZ和“TWS+TWLZ”组合鞣制体系的鞣制效果。
(2)本发明构建的三元生态皮革无铬鞣制体系，可以获得鞣制充分均匀、等电点高、阳电性强、对染整材料吸收好且革身柔软的皮革，赋予皮革更宽的使用范围和更优的品质，这是现有技术难以达到的效果。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明了，下面结合具体实施方式，对本发明进一步详细说明。应该理解，这些描述只是示例性的，而并非要限制本发明的范围。此外，在以下说明中，省略了对公知结构和技术的描述，以避免不必要地混淆本发明的概念。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本发明提供的实施方式为，生态皮革无铬鞣制工艺，以浸酸裸皮为原料，先使用无铬有机鞣剂TWS鞣制，加入木质素磺酸钠反应后，再使用无铬金属鞣剂TWLZ鞣制。
现有技术中TWS鞣剂和TWLZ鞣剂难以通过简单的组合获得鞣制充分均匀、等电点高、柔软度好的皮革，其原因在于，TWLZ是一种酸度较高的鞣剂，溶解后鞣液的pH通常小于3.0，如此低的pH条件下，TWS鞣革会发生明显退鞣，使得TWS鞣剂对纤维的分散和固定作用减弱，TWLZ鞣剂难于均匀渗透入皮中，最终导致鞣革收缩温度不足，成革柔软度不佳。申请人在实验中意外发现，TWS鞣制结束后加入木质素磺酸钠，不仅可以抑制TWS鞣剂退鞣，而且还能促进TWLZ鞣剂在皮中均匀分布，其反应机理为：木质素磺酸钠的分子结构中含有酚羟基和磺酸基等活性官能团，其酚羟基可以与TWS鞣剂和皮胶原形成多点氢键结合， 同时其苯环的疏水性也对TWS鞣剂形成了固定作用，通过结合鞣制的协同作用，使得TWS鞣革在低pH条件下也不会发生退鞣，导致胶原纤维始终处于分散状态，使得TWLZ鞣剂可以通过纤维孔道均匀渗透入皮中，提高TWLZ鞣剂在皮中的分布均匀性。此外，TWLZ鞣剂可与木质素磺酸钠中的磺酸基形成配位结合，在皮胶原纤维中形成稳固的交联网络结构，最终获得收缩温度高、柔软度好的皮革产品。
需要说明的是，所述浸酸裸皮为按照本领域常规工艺得到的浸酸裸皮，在一些优选实施方式中，所述浸酸裸皮包含但不限于浸酸绵羊皮、浸酸山羊皮和浸酸牛皮中任一种。
在一些优选方式中，以浸灰裸皮重量计，所述无铬有机鞣剂TWS的添加量为1-5wt％，所述木质素磺酸钠的添加量为1-4wt％，所述无铬金属鞣剂TWLZ的添加量为2-6wt％。需要说明的是，这三种成分用量均为现有技术中常规用量，非本发明的区别技术特征。
无铬有机鞣剂TWS进行鞣制是将无铬有机鞣剂TWS在浸酸裸皮中渗透2-4h，提碱至7.0-8.5，35-42℃下结合1-3h。例如在一些具体的实施方式中，将按常规工艺得到的浸酸裸皮置于转鼓中，加入以浸灰裸皮重量计为30-100wt％的浸酸液和1-5wt％的无铬有机鞣剂TWS，转动2-4h，提碱至pH为7.0-8.5后，补加以浸灰裸皮重量计为100-200wt％的热水，使浴液温度保持在35-42℃，转动1-3h，停鼓过夜，次日转0.5h后，排液。
无铬金属鞣剂TWLZ是在pH 3.0-4.5渗透1-4h，提碱至pH 3.5-4.5，35-42℃下结合1-4h。例如在一些具体实施方式中，调节浴液pH至3.0-4.5后，加入以浸灰裸皮重量计2-6wt％的无铬金属鞣剂TWLZ，继续转动1-4h，用提碱剂提碱至pH为3.5-4.5，补加以浸灰裸皮重量计100-200wt％的热水，使浴液温度保持在35-42℃，转动1-4h，停鼓过夜，次日转0.5h后，出鼓。
在一些优选实施方式中，加入木质素磺酸钠反应的具体方法为，向经过无铬有机鞣剂TWS鞣制的混合物中加入以浸灰裸皮重量计30-100wt％的常温水和1-4wt％的木质素磺酸钠，转动0.5-2h。
采用提碱剂进行提碱，在一些优选实施方式中，所述提碱剂包含但不限于碳酸氢钠、碳酸钠、氧化镁和自动提碱剂中任一种或多种。
为更好地理解本发明提供的技术方案，下述以多个具体实例分别说明应用本发明上述实施方式提供的生态皮革无铬鞣制工艺，及性能测试。
以下实施例和对比例中，TWLZ鞣剂在皮革中分布均匀度的测定方法为：
采用冷冻切片机将鞣制白湿革均匀剖分为粒面层、中间层和肉面层，102±2℃下烘干至恒重，然后称取一定质量的绝干皮样于消解管中，加入硝酸和双氧水，经微波消解仪消解 后，定容，然后用电感耦合等离子体发生光谱仪测定各层样品中的金属离子含量。TWLZ鞣剂在白湿革中分布均匀度的计算公式如下：
Figure PCTCN2022092095-appb-000001
以下实施例和对比例中，鞣制白湿革等电点的测定方法为：
将皮样放入45℃的烘箱中进行干燥，然后用研磨机将干燥后的皮样粉碎成2mm左右的皮粉。取10g皮粉和400mL水于500mL锥形瓶中，形成悬浮液，用0.1mol/L的HCl/NaOH调节悬浮液pH，然后将其放入温度为30℃的水浴振荡器中，于150r/min的转速下振荡30min后取出，用Zeta电位测定仪测定样品Zeta电位。绘制Zeta电位随时间的变化曲线，Zeta电位为零时悬浮液pH即为白湿革的等电点。
以下实施例和对比例中，鞣制白湿革收缩温度的测定方法为：
采用收缩温度仪测定白湿革的收缩温度。
以下实施例和对比例中，坯革柔软度的测定方法为：
将鞣制白湿革按照常规工艺进行染整，制得坯革，采用软度仪测定坯革的柔软度。
本发明具体实施例中采用的部分物质信息可以如下：
无铬有机鞣剂TWS：四川亭江新材料股份有限公司；
无铬金属鞣剂TWLZ：四川亭江新材料股份有限公司；
木质素磺酸钠：高唐华东木质素有限公司；
自动提碱剂：斯塔尔精细涂料(苏州)有限公司生产的MGO、四川德赛尔新材料科技有限公司生产的MO和四川亭江新材料股份有限公司生产的TJ-A511。
实施例1
将按常规工艺得到的浸酸牛皮置于转鼓中，加入以浸灰裸皮重量计为60wt％的浸酸液和5wt％的无铬有机鞣剂TWS，转动3h，用碳酸钠和碳酸氢钠提碱至pH为7.7后，补加以浸灰裸皮重量计为150wt％的热水，使浴液温度保持在42℃，转动2h，停鼓过夜，次日转0.5h后，排液；向转鼓中加入以浸灰裸皮重量计30wt％的常温水和2.5wt％的木质素磺酸钠，转动1.2h，用甲酸调节浴液pH至3.8后，加入以浸灰裸皮重量计4wt％的无铬金属鞣剂TWLZ，继续转动4h，用自动提碱剂MGO提碱至pH为4.0，补加以浸灰裸皮重量计200wt％的热水，使浴液温度保持在38℃，转动4h，停鼓过夜，次日转0.5h后，出鼓，得到生态无铬鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为99.6％，白湿革的等电点为6.9，白湿革 的收缩温度为92.6℃，染整后坯革的柔软度为7.7mm，检测结果如表1所示。
对比例1
与实施例1的区别在于，对比例1仅采用5wt％的TWS鞣剂进行鞣制，未采用木质素磺酸钠和TWLZ鞣剂进行鞣制，详细的工艺步骤为：
将按常规工艺得到的浸酸牛皮置于转鼓中，加入以浸灰裸皮重量计为60wt％的浸酸液和5wt％的无铬有机鞣剂TWS，转动3h，用碳酸钠和碳酸氢钠提碱至pH为7.7后，补加以浸灰裸皮重量计为150wt％的热水，使浴液温度保持在42℃，转动2h，停鼓过夜，次日转0.5h后，出鼓，得到鞣制白湿革。
经测定，白湿革的等电点为4.9，白湿革的收缩温度为84.5℃，染整后坯革的柔软度为7.0mm，检测结果如表1所示。
对比例2
与实施例1的区别在于，对比例2采用了9wt％的TWS鞣剂进行鞣制，未采用木质素磺酸钠和TWLZ鞣剂进行鞣制，详细的工艺步骤为：
将按常规工艺得到的浸酸牛皮置于转鼓中，加入以浸灰裸皮重量计为60wt％的浸酸液和9wt％的无铬有机鞣剂TWS，转动3h，用碳酸钠和碳酸氢钠提碱至pH为7.7后，补加以浸灰裸皮重量计为150wt％的热水，使浴液温度保持在42℃，转动2h，停鼓过夜，次日转0.5h后，出鼓，得到鞣制白湿革。
经测定，白湿革的等电点为5.0，白湿革的收缩温度为85.6℃，染整后坯革的柔软度为7.1mm，检测结果如表1所示。
对比例3
与实施例1的区别在于，对比例3仅采用4wt％的TWLZ鞣剂进行鞣制，未采用TWS鞣剂和木质素磺酸钠进行鞣制，详细的工艺步骤为：
将按常规工艺得到的浸酸牛皮置于转鼓中，加入以浸灰裸皮重量计为60wt％的浸酸液和4wt％的无铬金属鞣剂TWLZ，转动4h，用自动提碱剂MGO提碱至pH为4.0，补加以浸灰裸皮重量计200wt％的热水，使浴液温度保持在38℃，转动4h，停鼓过夜，次日转0.5h后，出鼓，得到鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为92.7％，白湿革的等电点为7.2，白湿革的收缩温度为69.2℃，染整后坯革的柔软度为5.4mm，检测结果如表1所示。
对比例4
与实施例1的区别在于，对比例4采用了9wt％的TWLZ鞣剂进行鞣制，未采用TWS鞣 剂和木质素磺酸钠进行鞣制，详细的工艺步骤为：
将按常规工艺得到的浸酸牛皮置于转鼓中，加入以浸灰裸皮重量计为60wt％的浸酸液和9wt％的无铬金属鞣剂TWLZ，转动4h，用自动提碱剂MGO提碱至pH为4.0，补加以浸灰裸皮重量计200wt％的热水，使浴液温度保持在38℃，转动4h，停鼓过夜，次日转0.5h后，出鼓，得到鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为93.2％，白湿革的等电点为7.4，白湿革的收缩温度为79.6℃，染整后坯革的柔软度为5.8mm，检测结果如表1所示。
对比例5
与实施例1的区别在于，对比例5虽采用“TWS+TWLZ”组合进行鞣制，但未采用木质素磺酸钠进行鞣制，详细的工艺步骤为：
将按常规工艺得到的浸酸牛皮置于转鼓中，加入以浸灰裸皮重量计为60wt％的浸酸液和5wt％的无铬有机鞣剂TWS，转动3h，用碳酸钠和碳酸氢钠提碱至pH为7.7后，补加以浸灰裸皮重量计为150wt％的热水，使浴液温度保持在42℃，转动2h，停鼓过夜，次日转0.5h后，排液；向转鼓中加入以浸灰裸皮重量计30wt％的常温水，用甲酸调节浴液pH至3.8后，加入以浸灰裸皮重量计4wt％的无铬金属鞣剂TWLZ，继续转动4h，用自动提碱剂MGO提碱至pH为4.0，补加以浸灰裸皮重量计200wt％的热水，使浴液温度保持在38℃，转动4h，停鼓过夜，次日转0.5h后，出鼓，得到鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为93.5％，白湿革的等电点为6.7，白湿革的收缩温度为83.8℃，染整后坯革的柔软度为6.2mm，检测结果如表1所示。
根据实施例1及对比例1-5的测试结果可以看出，对比例1采用4wt％的TWS鞣剂进行鞣制，白湿革的等电点仅为4.9，收缩温度为84.5℃，坯革柔软度为7.0mm；对比例2采用9wt％的TWS鞣剂进行鞣制，白湿革的等电点仅为5.0，收缩温度为85.6℃，坯革柔软度为7.1mm；对比例3采用5wt％的TWLZ鞣剂进行鞣制，TWLZ分布均匀度为92.7％，白湿革等电点为7.2，收缩温度仅为69.2℃，坯革柔软度低至5.4mm；对比例4采用9wt％的TWLZ鞣剂进行鞣制，TWLZ分布均匀度为93.2％，白湿革等电点为7.4，收缩温度仅为79.6℃，坯革柔软度低至5.8mm；对比例5采用“4wt％的TWS+5wt％的TWLZ”鞣制组合后，TWLZ分布均匀度为93.5％，白湿革等电点为6.7，收缩温度为83.8℃，坯革柔软度为6.2mm；实施例1采用“4wt％的TWS+木质素磺酸钠+5wt％的TWLZ”鞣制组合后，TWLZ分布均匀度高达99.6％，等电点为6.9，白湿革收缩温度和坯革柔软度也分别提升至92.6℃和7.7mm。
通过上述实施例和对比例的结果可以说明，单独的TWS鞣革等电点低，但柔软度好；单独TWLZ鞣革等电点高，但柔软度差；简单的采用“TWS+TWLZ”组合鞣革，虽然鞣革已具备较高的等电点，但由于TWS鞣革在低pH条件下会发生明显退鞣，使得鞣剂对纤维的分散和固定作用减弱，难于提升TWLZ分布均匀度，最终导致鞣革收缩温度和坯革柔软度均较低；而采用“TWS+木质素磺酸钠+TWLZ”组合鞣革，由于木质素磺酸钠通过其苯环的疏水作用和其羟基形成的多点氢键结构，对TWS鞣剂形成了固定作用，使得胶原纤维处于分散状态，因此TWLZ分布均匀度明显提升，白湿革的等电点和收缩温度均较高，柔软度甚至超过了单独TWS鞣制坯革。需要特别说明的是，只有在鞣制工艺中巧妙的引入木质素磺酸钠后，鞣革才能同时兼具TWS和TWLZ鞣制体系的优点，获得等电点高，柔软度好的皮革产品，而简单的采用“TWS+TWLZ”组合则难以达到本发明想要达到的技术效果。因此，本发明所使用的“TWS+木质素磺酸钠+TWLZ”三元鞣制工艺体系同现有技术相比具有显著的进步，能够产生有益的鞣制效果，克服现有鞣制体系鞣制性能的缺陷。
表1测试结果
  实施例1 对比例1 对比例2 对比例3 对比例4 对比例5
TWLZ分布均匀度(％) 99.6 不适用 不适用 92.7 93.2 93.5
白湿革等电点 6.9 4.9 5.0 7.2 7.4 6.7
白湿革收缩温度(℃) 92.6 84.5 85.6 69.2 79.6 83.8
坯革柔软度(mm) 7.7 7.0 7.1 5.4 5.8 6.2
实施例2
将按常规工艺得到的浸酸山羊皮置于转鼓中，加入以浸灰裸皮重量计为100wt％的浸酸液和3wt％的无铬有机鞣剂TWS，转动4h，用碳酸钠和碳酸氢钠提碱至pH为8.5后，补加以浸灰裸皮重量计为200wt％的热水，使浴液温度保持在35℃，转动1h，停鼓过夜，次日转0.5h后，排液；向转鼓中加入以浸灰裸皮重量计60wt％的常温水和1wt％的木质素磺酸钠，转动2h，用甲酸调节浴液pH至4.5后，加入以浸灰裸皮重量计6wt％的无铬金属鞣剂TWLZ，继续转动1h，用碳酸氢钠提碱至pH为4.5，补加以浸灰裸皮重量计100wt％的热水，使浴液温度保持在42℃，转动1h，停鼓过夜，次日转0.5h后，出鼓，得到生态无铬鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为98.5％，白湿革的等电点为7.5，白湿革的收缩温度为96.9℃，染整后坯革的柔软度为8.4mm。
实施例3
将按常规工艺得到的浸酸绵羊皮置于转鼓中，加入以浸灰裸皮重量计为30wt％的浸酸液和1wt％的无铬有机鞣剂TWS，转动2h，用碳酸钠和碳酸氢钠提碱至pH为7.0后，补加以浸灰裸皮重量计为100wt％的热水，使浴液温度保持在38℃，转动3h，停鼓过夜，次日转0.5h后，排液；向转鼓中加入以浸灰裸皮重量计100wt％的常温水和4wt％的木质素磺酸钠，转动0.5h，用甲酸调节浴液pH至3.0后，加入以浸灰裸皮重量计2wt％的无铬金属鞣剂TWLZ，继续转动2.5h，用碳酸钠提碱至pH为3.5，补加以浸灰裸皮重量计150wt％的热水，使浴液温度保持在35℃，转动2.5h，停鼓过夜，次日转0.5h后，出鼓，得到生态无铬鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为98.8％，白湿革的等电点为6.7，白湿革的收缩温度为90.4℃，染整后坯革的柔软度为7.8mm。
实施例4
将按常规工艺得到的浸酸牛皮置于转鼓中，加入以浸灰裸皮重量计为30wt％的浸酸液和1wt％的无铬有机鞣剂TWS，转动4h，用碳酸钠和碳酸氢钠提碱至pH为8.5后，补加以浸灰裸皮重量计为100wt％的热水，使浴液温度保持在35℃，转动3h，停鼓过夜，次日转0.5h后，排液；向转鼓中加入以浸灰裸皮重量计60wt％的常温水和4wt％的木质素磺酸钠，转动2h，用甲酸调节浴液pH至3.0后，加入以浸灰裸皮重量计6wt％的无铬金属鞣剂TWLZ，继续转动2.5h，用氧化镁提碱至pH为3.5，补加以浸灰裸皮重量计150wt％的热水，使浴液温度保持在35℃，转动1h，停鼓过夜，次日转0.5h后，出鼓，得到生态无铬鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为97.9％，白湿革的等电点为7.4，白湿革的收缩温度为91.3℃，染整后坯革的柔软度为7.6mm。
实施例5
将按常规工艺得到的浸酸绵羊皮置于转鼓中，加入以浸灰裸皮重量计为60wt％的浸酸液和3wt％的无铬有机鞣剂TWS，转动3h，用碳酸钠和碳酸氢钠提碱至pH为7.7后，补加以浸灰裸皮重量计为200wt％的热水，使浴液温度保持在35℃，转动1h，停鼓过夜，次日转0.5h后，排液；向转鼓中加入以浸灰裸皮重量计30wt％的常温水和1wt％的木质素磺酸钠，转动1.2h，用甲酸调节浴液pH至4.5后，加入以浸灰裸皮重量计4wt％的无铬金属鞣剂TWLZ，继续转动4h，用碳酸氢钠和氧化镁提碱至pH为4.5，补加以浸灰裸皮重量计100wt％的热水，使浴液温度保持在42℃，转动4h，停鼓过夜，次日转0.5h后，出鼓，得到生态无铬鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为99.1％，白湿革的等电点为7.0，白湿革的收缩温度为98.8℃，染整后坯革的柔软度为8.7mm。
实施例6
将按常规工艺得到的浸酸山羊皮置于转鼓中，加入以浸灰裸皮重量计为100wt％的浸酸液和5wt％的无铬有机鞣剂TWS，转动2h，用碳酸钠和碳酸氢钠提碱至pH为7.0后，补加以浸灰裸皮重量计为150wt％的热水，使浴液温度保持在42℃，转动2h，停鼓过夜，次日转0.5h后，排液；向转鼓中加入以浸灰裸皮重量计100wt％的常温水和2.5wt％的木质素磺酸钠，转动0.5h，用甲酸调节浴液pH至3.8后，加入以浸灰裸皮重量计2wt％的无铬金属鞣剂TWLZ，继续转动1h，用碳酸钠和自动提碱剂MO提碱至pH为4.0，补加以浸灰裸皮重量计200wt％的热水，使浴液温度保持在38℃，转动2.5h，停鼓过夜，次日转0.5h后，出鼓，得到生态无铬鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为98.4％，白湿革的等电点为6.6，白湿革的收缩温度为95.4℃，染整后坯革的柔软度为8.2mm。
实施例7
将按常规工艺得到的浸酸牛皮置于转鼓中，加入以浸灰裸皮重量计为100wt％的浸酸液和3wt％的无铬有机鞣剂TWS，转动2h，用碳酸钠和碳酸氢钠提碱至pH为7.0后，补加以浸灰裸皮重量计为200wt％的热水，使浴液温度保持在38℃，转动1h，停鼓过夜，次日转0.5h后，排液；向转鼓中加入以浸灰裸皮重量计100wt％的常温水和1wt％的木质素磺酸钠，转动0.5h，用甲酸调节浴液pH至4.5后，加入以浸灰裸皮重量计2wt％的无铬金属鞣剂TWLZ，继续转动1h，用碳酸氢钠和自动提碱剂TJ-A511提碱至pH为4.5，补加以浸灰裸皮重量计100wt％的热水，使浴液温度保持在42℃，转动2.5h，停鼓过夜，次日转0.5h后，出鼓，得到生态无铬鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为97.6％，白湿革的等电点为6.5，白湿革的收缩温度为90.8℃，染整后坯革的柔软度为7.4mm。
实施例8
将按常规工艺得到的浸酸绵羊皮置于转鼓中，加入以浸灰裸皮重量计为30wt％的浸酸液和5wt％的无铬有机鞣剂TWS，转动4h，用碳酸钠和碳酸氢钠提碱至pH为8.5后，补加以浸灰裸皮重量计为150wt％的热水，使浴液温度保持在42℃，转动2h，停鼓过夜，次日转0.5h后，排液；向转鼓中加入以浸灰裸皮重量计60wt％的常温水2.5wt％的木质素磺酸钠，转动2h，用甲酸调节浴液pH至3.8后，加入以浸灰裸皮重量计6wt％的无铬金属鞣剂 TWLZ，继续转动4h，用碳酸氢钠和自动提碱剂TJ-A511提碱至pH为4.0，补加以浸灰裸皮重量计200wt％的热水，使浴液温度保持在38℃，转动1h，停鼓过夜，次日转0.5h后，出鼓，得到生态无铬鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为99.4％，白湿革的等电点为7.5，白湿革的收缩温度为100.2℃，染整后坯革的柔软度为8.8mm。
实施例9
将按常规工艺得到的浸酸山羊皮置于转鼓中，加入以浸灰裸皮重量计为60wt％的浸酸液和1wt％的无铬有机鞣剂TWS，转动3h，用碳酸钠和碳酸氢钠提碱至pH为7.7后，补加以浸灰裸皮重量计为100wt％的热水，使浴液温度保持在38℃，转动3h，停鼓过夜，次日转0.5h后，排液；向转鼓中加入以浸灰裸皮重量计30wt％的常温水4wt％的木质素磺酸钠，转动1.2h，用甲酸调节浴液pH至3.0后，加入以浸灰裸皮重量计4wt％的无铬金属鞣剂TWLZ，继续转动2.5h，用碳酸钠、碳酸氢钠和自动提碱剂MO提碱至pH为3.5，补加以浸灰裸皮重量计150wt％的热水，使浴液温度保持在35℃，转动4h，停鼓过夜，次日转0.5h后，出鼓，得到生态无铬鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为98.3％，白湿革的等电点为7.0，白湿革的收缩温度为94.1℃，染整后坯革的柔软度为7.9mm。
实施例10
将按常规工艺得到的浸酸牛皮置于转鼓中，加入以浸灰裸皮重量计为60wt％的浸酸液和3wt％的无铬有机鞣剂TWS，转动3h，用碳酸钠和碳酸氢钠提碱至pH为8.5后，补加以浸灰裸皮重量计为200wt％的热水，使浴液温度保持在42℃，转动3h，停鼓过夜，次日转0.5h后，排液；向转鼓中加入以浸灰裸皮重量计60wt％的常温水4wt％的木质素磺酸钠，转动2h，用甲酸调节浴液pH至3.0后，加入以浸灰裸皮重量计6wt％的无铬金属鞣剂TWLZ，继续转动2.5h，用自动提碱剂MGO提碱至pH为4.5，补加以浸灰裸皮重量计200wt％的热水，使浴液温度保持在42℃，转动2.5h，停鼓过夜，次日转0.5h后，出鼓，得到生态无铬鞣制白湿革。
经测定，TWLZ鞣剂在白湿革中的分布均匀度为99.0％，白湿革的等电点为7.3，白湿革的收缩温度为93.7℃，染整后坯革的柔软度为7.9mm。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，但本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同 替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (8)

  1. 生态皮革无铬鞣制工艺，其特征在于，以浸酸裸皮为原料，先使用TWS鞣剂鞣制，加入木质素磺酸钠反应后，再使用TWLZ鞣剂鞣制。
  2. 如权利要求1所述的生态皮革无铬鞣制工艺，其特征在于，以浸灰裸皮重量计，所述TWS鞣剂的添加量为1-5wt％，所述木质素磺酸钠的添加量为1-4wt％，所述TWLZ鞣剂的添加量为2-6wt％。
  3. 如权利要求1所述的生态皮革无铬鞣制工艺，其特征在于，所述TWS鞣剂鞣制是将TWS鞣剂渗透2-4h，提碱至7.0-8.5，35-42℃下结合1-3h。
  4. 如权利要求1所述的生态皮革无铬鞣制工艺，其特征在于，所述TWLZ鞣剂是在pH 3.0-4.5渗透1-4h，提碱至pH 3.5-4.5，35-42℃下结合1-4h。
  5. 如权利要求1所述的生态皮革无铬鞣制工艺，其特征在于，加入木质素磺酸钠在常温下反应0.5-2h。
  6. 如权利要求1所述的生态皮革无铬鞣制工艺，其特征在于，所述浸酸裸皮包含但不限于浸酸绵羊皮、浸酸山羊皮和浸酸牛皮中任一种。
  7. 如权利要求3或4所述的生态皮革无铬鞣制工艺，其特征在于，采用提碱剂进行提碱，所述提碱剂包含但不限于碳酸氢钠、碳酸钠、氧化镁和自动提碱剂中任一种或多种。
  8. 采用如权利要求1-7任一所述无铬鞣制工艺得到的生态皮革。
PCT/CN2022/092095 2022-02-24 2022-05-11 生态皮革无铬鞣制工艺 WO2023159773A1 (zh)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103060488A (zh) * 2012-12-26 2013-04-24 四川亭江新材料股份有限公司 一种环保型坯革生产方法
CN107502687A (zh) * 2017-08-24 2017-12-22 南通双狮化工有限公司 一种复合树脂鞣剂
CN108690887A (zh) * 2018-07-25 2018-10-23 合肥盛达服装辅料有限公司 一种提高生皮鞣制效果的环保型鞣剂
EP3453728A1 (en) * 2017-09-06 2019-03-13 Exploitatiemaatschappij Smit-Vecht B.V. A method for manufacturing a lignin-modified polyphenolic product and its use for the treatment of leather and skin
CN110628968A (zh) * 2019-10-26 2019-12-31 辛集市凌爵皮革有限责任公司 绵羊皮革无铬鞣的加工工艺及绵羊白湿皮与绵羊皮革
CN112941248A (zh) * 2021-02-01 2021-06-11 辛集市梅花皮业有限公司 一种绵羊裘革及其无铬鞣的加工工艺
CN114410855A (zh) * 2022-02-24 2022-04-29 四川大学 生态皮革无铬鞣制工艺
CN114410853A (zh) * 2022-02-24 2022-04-29 四川大学 生态裘皮无铬鞣制工艺

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109797256B (zh) * 2019-02-18 2022-03-15 福建漳州市德昌皮业有限公司 牛皮皮革的加工工艺及其用于牛皮的鞣剂

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103060488A (zh) * 2012-12-26 2013-04-24 四川亭江新材料股份有限公司 一种环保型坯革生产方法
CN107502687A (zh) * 2017-08-24 2017-12-22 南通双狮化工有限公司 一种复合树脂鞣剂
EP3453728A1 (en) * 2017-09-06 2019-03-13 Exploitatiemaatschappij Smit-Vecht B.V. A method for manufacturing a lignin-modified polyphenolic product and its use for the treatment of leather and skin
CN108690887A (zh) * 2018-07-25 2018-10-23 合肥盛达服装辅料有限公司 一种提高生皮鞣制效果的环保型鞣剂
CN110628968A (zh) * 2019-10-26 2019-12-31 辛集市凌爵皮革有限责任公司 绵羊皮革无铬鞣的加工工艺及绵羊白湿皮与绵羊皮革
CN112941248A (zh) * 2021-02-01 2021-06-11 辛集市梅花皮业有限公司 一种绵羊裘革及其无铬鞣的加工工艺
CN114410855A (zh) * 2022-02-24 2022-04-29 四川大学 生态皮革无铬鞣制工艺
CN114410853A (zh) * 2022-02-24 2022-04-29 四川大学 生态裘皮无铬鞣制工艺

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