Preparation method of low-cytotoxicity ecological leather based on all-natural materials

Abstract

The invention relates to a preparation method of low-cytotoxicity ecological leather based on all-natural materials. Comprising the following steps of batch grouping, pre-soaking, fleshing and trimming, main soaking, fleshing and trimming, enzyme unhairing, liming, splitting and trimming, deliming, softening, pickling, tanning by combining tara tannin extract, tea polyphenol and zeolite, wringing, shaving and buffing, rewetting, primary neutralizing, fat liquoring, drying and finishing, and finishing. According to the tanning method, a tanning agent can be better combined with leather fibers by adopting a tanning extract-tea polyphenol-zeolite combined tanning method, so that the shrinkage temperature and the damp-heat resistance stability of the leather are improved, and the strength and the wear resistance of the leather are enhanced. Meanwhile, the tea polyphenol has the effects of resisting oxidation, resisting bacteria and the like, the aging resistance and the antibacterial performance of the leather can be improved, and the service life of the leather is prolonged.

Description

[0001] A method for preparing low-cytotoxic eco-leather based on all-natural materials Technical Field

[0002] This invention relates to the field of leather manufacturing technology, and in particular to a method for preparing low-cytotoxic eco-leather based on all-natural materials. Background Technology

[0003] Leather is a modified, rot-resistant material obtained by processing animal hides through physical and chemical processes such as hair removal and tanning. It is composed of natural protein fibers tightly woven in three-dimensional space, with a special grain layer on the surface. It has natural grain, luster and a comfortable feel, and also has high strength, good breathability and abrasion resistance. Therefore, it is widely used in clothing, footwear, bags, automotive interiors, furniture and many other fields.

[0004] Thanks to its natural animal hide origin, conventional leather possesses certain ecological properties, offering users advantages in terms of safety, skin-friendliness, and comfort. However, in current leather-making technologies, most processes utilize leather chemicals derived from petrochemical products. The application of such materials has significant drawbacks: firstly, they can easily lead to the presence of potentially harmful substances in the leather-making process and the final product, posing safety hazards; secondly, the use of petrochemical materials results in high carbon emissions during the leather-making process, and the produced leather products have low biochar content and poor biodegradability, making them insufficiently environmentally friendly.

[0005] Therefore, there is an urgent need for a technical solution that can improve the ecological and safety performance of leather, hence this case. Summary of the Invention

[0006] This invention provides a method for preparing low-cytotoxic eco-leather based on all-natural materials, in order to solve the problems of existing leather chemical materials having residual potentially harmful substances and poor biodegradability.

[0007] The present invention adopts the following technical solution: A method for preparing low-cytotoxic eco-leather based on all-natural materials includes the following steps: batching → pre-soaking → fleshing and trimming → main soaking → fleshing and trimming → enzymatic hair removal → liming → splitting and trimming → deliming → softening → acid soaking → tanning with tannin-tea polyphenols-zeolite combination → squeezing, leveling, and sanding → rewetting → primary neutralization → fatliquoring → drying and finishing → finishing; wherein, Batching: Using wet cowhide as raw material, select groups with basically the same weight, area, and color as a group, weigh them, and add 130% to the weight for measurement; Pre-soaking: Place the batched, salted, wet beef hides into a drum, add 200% water at 19-21℃, 0.2-0.3% tea saponin cleaning agent, 0.2-0.3% ProSpread penetrant (Proviera, USA), 0.1-0.2% degreasing agent (ProDegreaze, Proviera, USA), and 0.3-0.5% wood ash. Rotate for 10 minutes, then stop for 30 minutes; maintain a rotation speed of 2-3 rpm; control the temperature at 19-21℃, pH at 6.3-6.7, and Baume degree at 8-9; repeat 4-6 times; wash with water, remove from the drum; then remove the hides and trim the edges. Main soaking: Place the pre-soaked, de-fleshed, and trimmed cowhide into a drum, add 200% water at 18-22℃, and rotate the drum at 3 rpm; add 0.2-0.3% tea saponin cleaning agent, 0.2-0.3% penetrant, 0.2-0.3% ProSoak soaking agent (Proviera, USA), and 0.2-0.3% degreasing agent, rotate for 10 minutes, then stop for 20 minutes; control the pH to 6.3-6.7, rotate the drum at 2-3 rpm, and repeat 1-3 times; add 0.2-0.4% wood ash and 0.1-0.3% Sichuan pepper bactericide, adjust the pH to 9.5-10.5, rotate for 10 minutes, then stop for 20 minutes; repeat 5-8 times until fully transparent and the cut is milky white; wash with water and remove from the drum; Enzymatic hair removal: The soaked cowhide, after primary soaking, fleshing, and trimming, is placed in a rotating drum. 100% 24-28℃ solution is added, and the drum speed is 6-8 rpm. The pH is adjusted to 9.0-9.5. 0.3% penetrant, 1.0-1.5% nano-negative ion powder (Lingshou County Baifei Mineral Products Processing Plant), and 0.7-1.3% compound enzyme A are added, and the drum is rotated for 30 minutes. 0.3-0.5% keratinase K is added, and the drum is rotated for another 30 minutes. The hair removal rate is checked. If the hair removal rate is greater than 90%, proceed to the next step; otherwise, continue rotating for 30-60 minutes. The hide is then washed, filtered, and drained. Lime impregnation: Place bovine hides with a hair removal rate >90% into a drum, add 100% water at 24-26℃, and rotate the drum at 3-5 rpm; add 0.3% penetrant and 2% lime, and rotate for 60 min; add 100% water at 24-26℃, 50% of a 20% wood ash solution, and 0.15-0.2% of a 30% sodium hydroxide solution, and rotate for 60 min; then rotate for 5 min, stop for 55 min, and repeat 5-8 times; wash with water and remove from the drum; Deliming: Place the dehaired and split bovine hide into a drum, add 50-100% water at 30-35℃, add 0.3% penetrant, add 0.7-1.0% non-ammonium organic acid deliming agent (BITOR DF, Unitek, Italy), and rotate for 15-30 minutes at 6 rpm; then add 0.7-1.5% non-ammonium organic acid deliming agent (BITOR DF, Unitek, Italy), and rotate for 15-30 minutes; adjust the pH to 8.0-8.5. Softening: Continue adding 0.2-0.5% ammonium-free softening enzyme CBK (Sichuan Dawei Chemical) and 0.3% degreasing agent, incubate for 10 minutes, then stop for 20 minutes; adjust the temperature to 30-32℃ and pH to 7.5-8.5, incubate for 10 minutes, then stop for 20 minutes; repeat 2-3 times. When the buttock incision shows no color change in phenolphthalein reagent, softening is considered complete; wash with water and remove from the drum; Acid soaking: Place the softened raw cow hide into a rotating drum, add 50-150% water at 23-25℃, add 7-10% sodium chloride, and rotate for 10 minutes at 8 rpm; adjust the Baumé degree to ≥7; while rotating, add 0.5-1.5% formic acid diluted with 8-10 times room temperature water, and rotate for 30 minutes; add 0.2-0.8% concentrated sulfuric acid diluted with 8-10 times room temperature water, adjust the pH to 2.5-3.0, and rotate for 60-180 minutes; control the liquid to 50%; then add 10% of a 20% wood ash solution in portions, and rotate for 30 minutes; adjust the pH to 5.5-6.0; add 4-6% sodium sulfate, and rotate for 60 minutes; Tannin-tea polyphenol-zeolite combined tanning: This process is carried out in the same solution as the pickling solution. Add 15-30% tannin (TRUPOTAN TR, TRUMPLER, Germany) and 10-20% tea polyphenols, and rotate for 240-480 minutes. After complete penetration, add 50% water at 40-50℃ and rotate for 60 minutes. Then, add 0.1% formic acid in portions and rotate for 30 minutes each time. Adjust the pH to 3.0-3.5 and rotate for 30 minutes. Add 3-5% zeolite tanning aid BITAN CF (Unitek, Italy) and rotate for 30-60 minutes. Add 3-5% zeolite tanning aid BITAN BS (Unitek, Italy) and rotate for 30-60 minutes. Add wood ash to adjust the pH to 5.4-5.6 and rotate for 60-120 minutes. Drain the solution and remove from the drum. Sanding: After squeezing out water and shaving evenly (to a thickness of 1.10-1.15mm), the wet white leather is laid flat and sanded with sandpaper from a sanding machine to make its grain surface regular and uniform.

[0008] Filling: Place the wet white leather, after squeezing out water, shaving, and sanding, into a rotating drum. Add 80-100% water and 1% sodium formate, and rotate for 15 minutes. Add 10% of a 20% wood ash solution to adjust the pH to 5.5-6.5. Add 3-5% protein filler BITAN F (Unitek, Italy) and 3-5% natural dyes, and rotate for 60-120 minutes. Adjust the pH to 4.3-4.8 with formic acid and rotate for 15 minutes. Wash with water and drain. Fat addition: Add 100-150% water at 45-55℃, 9-18% sulfated tea oil, 2% sulfated cow hoof oil BITIOL CK (Unitek, Italy), 2% lecithin fatliquoring agent BITIOL LC (Unitek, Italy), and 4% natural compound fatliquoring agent BITIOL CO (Unitek, Italy). Incubate for 90 minutes, then adjust the pH to 3.6-3.8 with formic acid and incubate for 30 minutes. Soak in a 300% glycerol aqueous solution (glycerol:water = 1:1-2) for 24 hours, wash with water, and remove from drum.

[0009] Furthermore, the above finishing process is as follows: dehydration and stretching → vacuum drying → hanging and drying → rehydration → softening by tumbling → stretching and drying → sealing the base → calendering → top coating (surface treatment) → softening → rolling → measuring and warehousing; the main operational points are as follows: Dewatering and stretching: Performed on a reciprocating dewatering and stretching machine with a blade spacing of 1.10-1.15 mm, a dewatering pressure of 30 bar, and a feed speed of 20-25 m / min; the moisture content after dewatering is controlled at 50-55%. Vacuum drying: carried out in a vacuum dryer at a temperature of 45℃ for 500 seconds and a negative pressure of 23-26 Mbar; the moisture content after vacuum drying is controlled at 23-30%. Hanging and drying: carried out on a hanging drying line, with a hanging time of 24 hours. The moisture content after hanging and drying is controlled at 13-18%. Drying: The drying process was carried out in a constant temperature and humidity drying oven. The temperatures of the three ovens were 37℃, 42℃ and 48℃, the humidity was 30-35% and the time was 12 hours. The moisture content after drying was controlled at 6-10%. Rehydration: Performed on a rehydration machine, the moisture content is controlled at 20-25% after rehydration; Tumbling and softening: This is carried out in a stainless steel octagonal tumbling and softening drum at a speed of 15 r / min for 6 hours. The drum rotates in both directions, and the internal temperature is automatically controlled at 25-30℃. After tumbling and softening, the moisture content of the raw leather is 18-20%. Stretching: Performed on a horizontal stretching machine, oven temperature 50 ℃, stretching distance 6 cm, clamping distance 10-12 cm, raw leather time in oven 20 min, raw leather moisture content 14%-18%; Base coat: Apply using a spray gun, with a coating amount of approximately 5-10 g / sf, spraying 1-3 times, each time 3-5 g / sf2, for a total coating amount of approximately 3-15 g / sf2. The coating agent formulation is as follows: 500-1000 parts water, 500-800 parts water-soluble protein binder (BI-596, Stahl GmbH, Germany), 200-300 parts modified protein Melio Top 286 and modified protein gloss agent Melio Top 239 (HM-443, Stahl GmbH, Germany), 20-100 parts penetrant ProSpread, and 50-100 parts bio-based additive (puRE130, Qingdao Baicaobian Biotechnology Co., Ltd.). Calendering: Performed on a board ironing machine at a board surface temperature of 100℃, a pressure of 30kg, and a time of 2s. Top Coating: Operate on a computer-controlled sprayer. The coating formula is as follows: 100-800 parts water, 10-20 parts graphene-modified silicone feel agent (silicone HM-443, Stahl GmbH, Germany), 10-20 parts graphene oxide dispersion (Shanghai Macklin Reagent); 20-40 parts γ-aminopropyltriethoxysilane (97%, Shanghai Macklin Reagent, freshly prepared) 50-100 parts; 200-400 parts modified protein brightener Melio Top 239 (HM-443, Stahl GmbH, Germany); 20-100 parts penetrant; 50-100 parts bio-based additive (puRE130, Qingdao Baicaobian Biotechnology Co., Ltd.); spray 1-3 times, 2-3 g / sf2 each time, with a coating amount of approximately 3-5 g / sf2. Oscillating softening: Operated on an oscillating softening machine. The parameters of the oscillating softening machine are: conveying speed 9.5 m / min, 5 stages; Blazing: Operated on a pass-through ironing machine, with a temperature of 120 ℃, a pressure of 20-30 kg, and a speed of 8 m / min.

[0010] Further, the preparation of the above-mentioned tea saponin cleaning agent is as follows: 1 kg of pulverized tea cake powder is added to a subcritical treatment device, 10-15 kg of 70-90% ethanol aqueous solution is added, the device is sealed, and the reaction is carried out at a temperature of 105-150℃ and a pressure of 0.5-1.5MPa for 0.5-3 hours. The mixture is filtered, and the filtrate is cooled to room temperature. 0.5-10% NaCl is added, and the mixture is centrifuged. The lower layer is evaporated to dryness to obtain tea saponin. Then, tea saponin is mixed with wood ash and acetic acid (Shandong Yicheng Biotechnology Co., Ltd.) to obtain the tea saponin cleaning agent.

[0011] Furthermore, the preparation of the above-mentioned plant ash involves: burning waste wood and residues from natural plant materials produced by this patented technology, collecting the ash, and crushing it. The plant ash is then poured into water, stirred, and impurities are filtered out to obtain a plant ash solution.

[0012] Further, the preparation of the above-mentioned zanthoxylum bactericide is as follows: 1 kg of dried and pulverized zanthoxylum leaf powder is added to a subcritical treatment device, 10-15 kg of 70-90% ethanol aqueous solution is added, the device is sealed, and the reaction is carried out at a temperature of 105-150℃ and a pressure of 0.5-1.5 MPa for 0.5-3 hours. The mixture is then filtered, the filtrate is collected, and the zanthoxylum bactericide is obtained after concentration.

[0013] Further, the above-mentioned tea polyphenols are prepared as follows: 1 kg of pulverized non-grade green tea powder is added to a subcritical treatment device, 15-45 kg of distilled water is added, the device is sealed, and the reaction is carried out at a temperature of 60-80℃ for 0.5-3 hours. The mixture is then filtered, and the filtrate is cooled to room temperature. After freeze-drying, tea polyphenols are obtained.

[0014] Further, the above-mentioned method for preparing sulfated tea oil involves: adding 1 kg of pulverized tea cake powder to a subcritical treatment device, adding 10-15 kg of 70-90% ethanol aqueous solution, sealing the device, reacting at a temperature of 105-150℃ and a pressure of 0.5-1.5 MPa for 0.5-3 hours, filtering, and cooling the filtrate to room temperature; adding 0.5-10% NaCl, centrifuging, and evaporating the upper layer to obtain tea oil, which is then subjected to conventional sulfation treatment to obtain a tea oil fatliquoring agent.

[0015] As can be seen from the above description of the present invention, compared with the prior art, the present invention has the following advantages: 1. Throughout the leather-making process, self-made natural materials are widely used. For example, tea saponin cleaning agent and wood ash are used in the pre-soaking stage, peppermint bactericide is added in the main soaking stage, natural dyes are used in the filling stage, and sulfated tea oil is used in the fatliquoring stage. Compared with traditional chemical agents, these natural materials cause less pollution to the environment, reducing the emission of harmful chemicals and lowering the potential harm to human health and the ecological environment during production and use.

[0016] 2. Traditional leather production processes use a large amount of chemical agents containing harmful substances such as heavy metals and formaldehyde. This solution uses natural materials to replace some of the chemical agents, reducing chemical pollution at the source. This aligns with the current green and environmentally friendly development concept and is conducive to the sustainable development of the leather industry.

[0017] 3. The innovative tanning process employs a combination of tannin-tea polyphenols-zeolite, allowing the tanning agents to better integrate with leather fibers. This improves the leather's shrinkage temperature and resistance to damp heat, enhancing its strength and abrasion resistance. Simultaneously, tea polyphenols possess antioxidant and antibacterial properties, further improving the leather's aging resistance and antibacterial performance, thus extending its lifespan.

[0018] 4. During the fatliquoring and filling stages, the addition of natural and modified fatliquoring agents such as sulfated tea oil, sulfated cow hoof oil, and lecithin fatliquoring agents, as well as natural dyes and fillers, enables the leather to achieve good softness and a full hand feel. These fatliquoring agents and fillers can be evenly distributed between the leather fibers, increasing the leather's elasticity and toughness, making the leather more comfortable and durable. Detailed Implementation

[0019] Example 1: A method for preparing low-cytotoxic eco-leather based on all-natural materials includes the following steps: batching → pre-soaking → fleshing and trimming → main soaking → fleshing and trimming → enzymatic hair removal → liming → splitting and trimming → deliming → softening → acid soaking → tanning with tannin-tea polyphenols-zeolite combination → squeezing, leveling, and sanding → rewetting → primary neutralization → fatliquoring → drying and finishing → finishing; wherein, Batching: Using wet cowhide as raw material, select groups with basically the same weight, area, and color as a group, weigh them, and add 130% to the weight for measurement; Pre-soaking: Place the batched salted beef hides into the drum, add 200% water at 19℃, 0.2% tea saponin cleaning agent, 0.2% ProSpread penetrant (Proviera, USA), 0.1% degreasing agent (ProDegreaze, USA), and 0.3% wood ash. Rotate for 10 minutes, stop for 30 minutes; speed 2 rpm; control temperature at 19℃, pH 6.3-6.7, Baume degree 8-9; repeat 4 times; wash with water, remove from the drum; remove the hides and trim the edges. Main soaking: Place the pre-soaked, de-fleshed, and trimmed cowhide into a drum, add 200% water at 18℃, and rotate the drum at 3 rpm; add 0.2% tea saponin cleaning agent, 0.2% penetrant, 0.2% ProSoak soaking agent (Proviera, USA), and 0.2% degreasing agent, rotate for 10 minutes, stop for 20 minutes; control the pH to 6.3-6.7, rotate at 2 rpm, and repeat once; add 0.2% wood ash and 0.1% Sichuan pepper bactericide, adjust the pH to 9.5-10.5, rotate for 10 minutes, stop for 20 minutes; repeat 5 times, requiring complete penetration and a milky white cut; wash with water and remove from the drum; Enzymatic hair removal: The soaked cowhide, after being soaked, de-fleshed, and trimmed, is placed into a rotating drum. 100% 24℃ solution is added, and the drum speed is 6 rpm. The pH is adjusted to 9.0-9.5. 0.3% penetrant, 1.0% nano-negative ion powder (Lingshou County Baifei Mineral Products Processing Plant), and 0.7% compound enzyme A are added, and the drum is rotated for 30 minutes. 0.3% keratinase K is added, and the drum is rotated for another 30 minutes. The hair removal rate is checked. If the hair removal rate is greater than 90%, proceed to the next step; otherwise, continue rotating for 30 minutes. The hide is then washed with water, the hair is filtered, and the solution is drained. Lime impregnation: Place bovine delimed hides with a hair removal rate >90% into a drum, add 100% water at 24℃, and rotate the drum at 3 rpm; add 0.3% penetrant and 2% lime, and rotate for 60 min; add 100% water at 24℃, 50% of a 20% wood ash solution, and 0.15% of a 30% sodium hydroxide solution, and rotate for 60 min; then rotate for 5 min, stop for 55 min, and repeat 5 times; wash with water and remove from the drum; Deliming: Place the dehaired and split bovine hide into a drum, add 50% water at 30℃, 0.3% penetrant, and 0.7% non-ammonium organic acid deliming agent (BITOR DF, Unitek, Italy). Rotate for 15 minutes at 6 rpm. Then add another 0.7% non-ammonium organic acid deliming agent (BITOR DF, Unitek, Italy) and rotate for 15-30 minutes. Adjust the pH to 8.0-8.5. Softening: Continue adding 0.2% ammonium-free softening enzyme CBK (Sichuan Dawei Chemical) and 0.3% degreasing agent, incubate for 10 minutes, then stop for 20 minutes; adjust the temperature to 30-32℃ and pH to 7.5-8.5, incubate for 10 minutes, then stop for 20 minutes; repeat twice. When the buttock incision shows no color change in phenolphthalein reagent, softening is considered complete; wash with water and remove from the drum; Acid soaking: Softened raw cowhide is placed into a rotary drum, 50% water at 23°C is added, 7% sodium chloride is added, and the drum is rotated for 10 minutes at 8 rpm; the Baumé degree is adjusted to ≥7; while rotating, 0.5% formic acid (diluted with 8 times the amount of room temperature water) is added, and the drum is rotated for 30 minutes; 0.2% concentrated sulfuric acid (diluted with 8 times the amount of room temperature water) is added, and the pH is adjusted to 2.5-3.0, and the drum is rotated for 60 minutes; the liquid is then controlled to 50%; then 10% of a 20% wood ash solution is added in portions, and the drum is rotated for 30 minutes; the pH is adjusted to 5.5-6.0; 4% sodium sulfate is added, and the drum is rotated for 60 minutes. Tannin-tea polyphenol-zeolite combined tanning: This process is carried out in the same solution as the pickling solution. Add 15% tannin (TRUPOTAN TR, TRUMPLER, Germany) and 10% tea polyphenols, and rotate for 240 minutes. After complete penetration, add 50% water at 40°C and rotate for 60 minutes. Then, add 0.1% formic acid in portions and rotate for 30 minutes each time. Adjust the pH to 3.0-3.5 and rotate for 30 minutes. Add 3% zeolite tanning agent BITAN CF (Unitek, Italy) and rotate for 30 minutes. Add 3% zeolite tanning agent BITAN BS (Unitek, Italy) and rotate for 300 minutes. Add wood ash to adjust the pH to 5.4-5.6 and rotate for 60 minutes. Drain the solution and remove from the drum. Sanding: After squeezing out water and shaving evenly (to a thickness of 1.10-1.15mm), the wet white leather is laid flat and sanded with sandpaper from a sanding machine to make its grain surface regular and uniform.

[0020] Filling: Place the wet white leather, after squeezing out water, shaving, and sanding, into a drum, add 80% water and 1% sodium formate, and rotate for 15 minutes; add 10% 20% wood ash solution to adjust the pH to 5.5, add 3% protein filler BITAN F (Unitek, Italy) and 3% natural dye, and rotate for 60 minutes; adjust the pH to 4.3-4.8 with formic acid, and rotate for 15 minutes; wash with water; drain. Fat addition: Add 100% water at 45℃, 9% sulfated tea oil, 2% sulfated cow hoof oil BITIOL CK (Unitek, Italy), 2% lecithin fatliquoring agent BITIOL LC (Unitek, Italy), and 4% natural compound fatliquoring agent BITIOL CO (Unitek, Italy). Incubate for 90 minutes, then adjust the pH to 3.6-3.8 with formic acid, incubate for 30 minutes, and soak in 300% glycerol aqueous solution (glycerol:water = 1:1-2) for 24 hours. Wash with water and remove from drum.

[0021] Furthermore, the above finishing process is as follows: dehydration and stretching → vacuum drying → hanging and drying → rehydration → softening by tumbling → stretching and drying → sealing the base → calendering → top coating (surface treatment) → softening → rolling → measuring and warehousing; the main operational points are as follows: Dewatering and stretching: Performed on a reciprocating dewatering and stretching machine with a blade spacing of 1.10 mm, a dewatering pressure of 30 bar, and a feed speed of 20 m / min; the moisture content after dewatering is controlled at 50%. Vacuum drying: carried out in a vacuum dryer at a temperature of 45℃ for 500 seconds and a negative pressure of 23 Mbar; the moisture content after vacuum drying is controlled at 23%. Hanging and drying: carried out on a hanging drying line, with a hanging time of 24 hours, and the moisture content after hanging and drying is controlled at 13%; Drying: The drying was carried out in a constant temperature and humidity drying oven. The temperatures of the three ovens were 37℃, 42℃ and 48℃, the humidity was 30%, and the time was 12 hours. The moisture content after drying was controlled at 6%. Re-humidification: carried out on a re-humidification machine, with the moisture content controlled at 20% after re-humidification; Tumbling and softening: This process is carried out in a stainless steel octagonal tumbling and softening drum at a speed of 15 r / min for 6 hours. The drum rotates in both directions, and the internal temperature is automatically controlled at 25℃. After tumbling and softening, the moisture content of the raw leather is 18%. Stretching: Performed on a horizontal stretching machine, oven temperature 50 ℃, stretching distance 6 cm, clamping distance 10 cm, raw leather time in oven 20 min, raw leather moisture content 14%; Base coat: Apply using a spray gun, with a coating amount of approximately 5g / sf, spraying 3 times, each time 3g / sf2, for a total coating amount of approximately 8g / sf2; the coating agent formula is as follows: 500 parts water, 500 parts water-soluble protein binder (BI-596 Stahl GmbH, Germany), 200 parts modified protein Melio Top 286, 200 parts modified protein gloss agent Melio Top 239 (HM-443 Stahl GmbH, Germany), 20 parts penetrant ProSpread, and 50 parts bio-based additive (puRE130 Qingdao Baicaobian Biotechnology Co., Ltd.); Calendering: Performed on a board ironing machine at a board surface temperature of 100℃, a pressure of 30kg, and a time of 2s. Top Coating: Operated on a computer-controlled sprayer. The coating formula is as follows: 100 parts water, 10 parts graphene-modified silicone feel agent (silicone HM-443, Stahl GmbH, Germany), 10 parts graphene oxide dispersion (Shanghai Macklin Reagent); 40 parts γ-aminopropyltriethoxysilane (97%, Shanghai Macklin Reagent, freshly prepared) 50 parts; 200 parts modified protein brightener MelioTop 239 (HM-443, Stahl GmbH, Germany); 20 parts penetrant; 50 parts bio-based additive (puRE130, Qingdao Baicaobian Biotechnology Co., Ltd.); spray 3 times, 2g / sf2 each time, with a coating amount of approximately 3 g / sf2. Oscillating softening: Operated on an oscillating softening machine. The parameters of the oscillating softening machine are: conveying speed 9.5 m / min, 5 stages; Blazing: Operated on a pass-through ironing machine, with a temperature of 120 ℃, a pressure of 20-30 kg, and a speed of 8 m / min.

[0022] Preparation of the above-mentioned tea saponin cleaning agent: 1 kg of crushed tea cake powder was added to a subcritical treatment device, 10 kg of 70% ethanol aqueous solution was added, the device was sealed, and the reaction was carried out at a temperature of 105℃ and a pressure of 0.5 MPa for 0.5 h. The mixture was filtered, and the filtrate was cooled to room temperature. 5% NaCl was added, and the mixture was centrifuged. The lower layer was evaporated to dryness to obtain tea saponin. Then, tea saponin was mixed with wood ash and acetic acid (Shandong Yicheng Biotechnology Co., Ltd.) to obtain the tea saponin cleaning agent.

[0023] Preparation of the above-mentioned wood ash: Waste wood and residues from natural plant materials produced by this patented technology are burned, the ash is collected and crushed. The wood ash is poured into water, stirred, and impurities are filtered out to obtain a wood ash solution.

[0024] Preparation of the above-mentioned zanthoxylum bactericide: 1 kg of dried and pulverized zanthoxylum leaf powder was added to a subcritical treatment device, 10 kg of 70% ethanol aqueous solution was added, the device was sealed, and the reaction was carried out at a temperature of 105℃ and a pressure of 1.5 MPa for 0.5 h. The mixture was filtered, the filtrate was collected, and the zanthoxylum bactericide was obtained after concentration.

[0025] Preparation of the above-mentioned tea polyphenols: 1 kg of pulverized non-grade green tea powder was added to a subcritical treatment device, 15 kg of distilled water was added, the device was sealed, and the reaction was carried out at 60℃ for 0.5 h. The mixture was filtered, and the filtrate was cooled to room temperature. After freeze-drying, tea polyphenols were obtained.

[0026] The above-mentioned method for preparing sulfated tea oil is as follows: 1 kg of crushed tea cake powder is added to a subcritical treatment device, 10 kg of 70% ethanol aqueous solution is added, the device is sealed, and the reaction is carried out at a temperature of 105℃ and a pressure of 0.5 MPa for 0.5 h. The mixture is then filtered, and the filtrate is cooled to room temperature. 0.5% NaCl is added, and the mixture is centrifuged. The upper layer is evaporated to dryness to obtain tea oil, which is then subjected to conventional sulfation treatment to obtain a tea oil fatliquoring agent.

[0027] Example 2: A method for preparing low-cytotoxic eco-leather based on all-natural materials includes the following steps: batching → pre-soaking → fleshing and trimming → main soaking → fleshing and trimming → enzymatic hair removal → liming → splitting and trimming → deliming → softening → acid soaking → tanning with tannin-tea polyphenols-zeolite combination → squeezing, leveling, and sanding → rewetting → primary neutralization → fatliquoring → drying and finishing → finishing; wherein, Batching: Using wet cowhide as raw material, select groups with basically the same weight, area, and color as a group, weigh them, and add 130% to the weight for measurement; Pre-soaking: Place the batched salted beef hides into the drum, add 200% water at 21°C, 0.3% tea saponin cleaning agent, 0.3% ProSpread penetrant (Proviera, USA), 0.2% degreasing agent (ProDegreaze, USA), and 0.5% wood ash. Rotate for 10 minutes, stop for 30 minutes; speed 3 rpm; control temperature at 21°C, pH 6.3-6.7, Baume degree 9; repeat 6 times; wash with water, remove from the drum; remove meat and trim edges; Main soaking: Place the pre-soaked, de-fleshed, and trimmed cowhide into a drum, add 200% water at 22℃, and rotate the drum at 3 rpm; add 0.3% tea saponin cleaning agent, 0.3% penetrant, 0.3% ProSoak soaking agent (Proviera, USA), and 0.3% degreasing agent, rotate for 10 minutes, stop for 20 minutes; control the pH to 6.3-6.7, rotate at 3 rpm, and repeat 3 times; add 0.4% wood ash and 0.3% Sichuan pepper bactericide, adjust the pH to 9.5-10.5, rotate for 10 minutes, stop for 20 minutes; repeat 8 times, requiring complete penetration and a milky white cut surface; wash with water and remove from the drum; Enzymatic hair removal: The soaked cowhide, after soaking, fleshing, and trimming, is placed into a rotating drum. 100% 28℃ solution is added, and the drum speed is 8 rpm. The pH is adjusted to 9.0-9.5. 0.3% penetrant, 1.5% nano-negative ion powder (Lingshou County Baifei Mineral Products Processing Plant), and 1.3% compound enzyme A are added, and the drum is rotated for 30 minutes. 0.5% keratinase K is added, and the drum is rotated for another 30 minutes. The hair removal rate is checked. If the hair removal rate is greater than 90%, proceed to the next step; otherwise, continue rotating for 30-60 minutes. The cowhide is then washed, the hair is filtered, and the solution is drained. Lime impregnation: Place bovine de-limed hides with a hair removal rate >90% into a drum, add 100% water at 26℃, and rotate the drum at 5 rpm; add 0.3% penetrant and 2% lime, and rotate for 60 min; add 100% water at 26℃, 50% of a 20% wood ash solution, and 0.2% of a 30% sodium hydroxide solution, and rotate for 60 min; then rotate for 5 min, stop for 55 min, and repeat 8 times; wash with water and remove from the drum; Deliming: Place the dehaired and split bovine hide into a drum, add 100% water at 35°C, 0.3% penetrant, and 1.0% non-ammonium organic acid deliming agent (BITOR DF, Unitek, Italy). Rotate for 30 minutes at 6 rpm. Then add 1.5% non-ammonium organic acid deliming agent (BITOR DF, Unitek, Italy) and rotate for 30 minutes. Adjust the pH to 8.0-8.5. Softening: Continue adding 0.5% ammonium-free softening enzyme CBK (Sichuan Dawei Chemical) and 0.3% degreasing agent, incubate for 10 minutes, then stop for 20 minutes; adjust the temperature to 32℃ and pH to 7.5-8.5, incubate for 10 minutes, then stop for 20 minutes; repeat 2-3 times. When the buttock incision shows no color change in phenolphthalein reagent, softening is considered complete; wash with water and remove from the drum; Acid soaking: Softened raw cowhide is placed into a rotary drum, 150% water at 25℃ is added, 10% sodium chloride is added, and the drum is rotated for 10 minutes at 8 rpm; the Baumé degree is adjusted to ≥7; while rotating, 1.5% formic acid (85% concentration) diluted with 10 times room temperature water is added, and the drum is rotated for 30 minutes; 0.8% concentrated sulfuric acid (98% concentration) diluted with 10 times room temperature water is added, and the pH is adjusted to 2.5-3.0, and the drum is rotated for 180 minutes; the liquid is controlled to 50%; then 10% of a 20% wood ash solution is added in portions, and the drum is rotated for 30 minutes; the pH is adjusted to 5.5-6.0; 6% sodium sulfate is added, and the drum is rotated for 60 minutes; Tannin-tea polyphenol-zeolite combined tanning: This process is carried out in the same solution as the pickling solution. Add 30% tannin (TRUPOTAN TR, TRUMPLER, Germany) and 20% tea polyphenols, and rotate for 480 min. After complete penetration, add 50% water at 50℃ and rotate for 60 min. Then add 0.1% formic acid in portions and rotate for 30 min each time. Adjust the pH to 3.0-3.5 and rotate for 30 min. Add 5% zeolite tanning agent BITAN CF (Unitek, Italy) and rotate for 60 min. Add 5% zeolite tanning agent BITAN BS (Unitek, Italy) and rotate for 60 min. Add wood ash to adjust the pH to 5.4-5.6 and rotate for 120 min. Drain the solution and remove from the drum. Sanding: After squeezing out water and shaving evenly (to a thickness of 1.10-1.15mm), the wet white leather is laid flat and sanded with sandpaper from a sanding machine to make its grain surface regular and uniform.

[0028] Filling: Place the wet white leather, after squeezing out water, shaving, and sanding, into a drum, add 100% water and 1% sodium formate, and rotate for 15 minutes; add 10% 20% wood ash solution to adjust the pH to 5.5-6.5, add 5% protein filler BITAN F (Unitek, Italy) and 5% natural dye, and rotate for 120 minutes; adjust the pH to 4.3-4.8 with formic acid, and rotate for 15 minutes; wash with water; drain. Fat addition: Add 150% water at 55℃, 18% sulfated tea oil, 2% sulfated cow hoof oil BITIOL CK (Unitek, Italy), 2% lecithin fatliquoring agent BITIOL LC (Unitek, Italy), and 4% natural compound fatliquoring agent BITIOL CO (Unitek, Italy). Incubate for 90 minutes, then adjust the pH to 3.6-3.8 with formic acid, incubate for 30 minutes, and soak in a 300% glycerol aqueous solution (glycerol:water = 1:1-2) for 24 hours. Wash with water and remove from drum.

[0029] Furthermore, the above finishing process is as follows: dehydration and stretching → vacuum drying → hanging and drying → rehydration → softening by tumbling → stretching and drying → sealing the base → calendering → top coating (surface treatment) → softening → rolling → measuring and warehousing; the main operational points are as follows: Dewatering and stretching: Performed on a reciprocating dewatering and stretching machine with a blade spacing of 1.15 mm, a dewatering pressure of 30 bar, and a feed speed of 25 m / min; the moisture content after dewatering is controlled at 55%. Vacuum drying: carried out in a vacuum dryer at a temperature of 45℃ for 500 seconds and a negative pressure of 23-26 Mbar; the moisture content after vacuum drying is controlled at 23-30%. Hanging and drying: carried out on a hanging drying line, with a hanging time of 24 hours, and the moisture content after hanging and drying is controlled at 18%; Drying: The drying process was carried out in a constant temperature and humidity drying oven. The temperatures of the three ovens were 37℃, 42℃ and 48℃, the humidity was 35%, and the drying time was 12 hours. The moisture content after drying was controlled at 10%. Re-humidification: carried out on a re-humidification machine, with the moisture content controlled at 25% after re-humidification; Tumbling and softening: This is carried out in a stainless steel octagonal tumbling and softening drum at a speed of 15 r / min for 6 hours. The drum rotates in both directions, and the internal temperature is automatically controlled at 30℃. After tumbling and softening, the moisture content of the raw leather is 20%. Stretching: Performed on a horizontal stretching machine, oven temperature 50 ℃, stretching distance 6 cm, clamping distance 12 cm, raw leather time in oven 20 min, raw leather moisture content 18%; Base coat: Apply using a spray gun, with a coating amount of approximately 10g / sf, spraying 3 times, each time 5g / sf2, for a total coating amount of approximately 15g / sf2; the coating agent formula is as follows: 1000 parts water, 800 parts water-soluble protein binder (BI-596 Stahl GmbH, Germany), 300 parts modified protein Melio Top 286, 300 parts modified protein gloss agent Melio Top 239 (HM-443 Stahl GmbH, Germany), 100 parts penetrant ProSpread, and 100 parts bio-based additive (puRE130 Qingdao Baicaobian Biotechnology Co., Ltd.); Calendering: Performed on a board ironing machine at a board surface temperature of 100℃, a pressure of 30kg, and a time of 2s. Top Coating: Operated on a computer-controlled sprayer. The coating formula is as follows: 800 parts water, 20 parts graphene-modified silicone feel agent (silicone HM-443, Stahl GmbH, Germany), 20 parts graphene oxide dispersion (Shanghai Macklin Reagent); 40 parts γ-aminopropyltriethoxysilane (97%, Shanghai Macklin Reagent, freshly prepared) 100 parts; 400 parts modified protein brightener MelioTop 239 (HM-443, Stahl GmbH, Germany); 100 parts penetrant; 100 parts bio-based additive (puRE130, Qingdao Baicaobian Biotechnology Co., Ltd.); spray 3 times, 3 g / sf2 each time, with a coating amount of approximately 5 g / sf2. Oscillating softening: Operated on an oscillating softening machine. The parameters of the oscillating softening machine are: conveying speed 9.5 m / min, 5 stages; Blazing: Operated on a pass-through ironing machine, with a temperature of 120 ℃, a pressure of 20-30 kg, and a speed of 8 m / min.

[0030] Preparation of the above-mentioned tea saponin cleaning agent: 1 kg of crushed tea cake powder was added to a subcritical treatment device, 15 kg of 90% ethanol aqueous solution was added, the device was sealed, and the reaction was carried out at a temperature of 150℃ and a pressure of 1.5 MPa for 3 hours. The mixture was filtered, and the filtrate was cooled to room temperature. 10% NaCl was added, and the mixture was centrifuged. The lower layer was evaporated to dryness to obtain tea saponin. Then, tea saponin was mixed with wood ash and acetic acid (Shandong Yicheng Biotechnology Co., Ltd.) to obtain the tea saponin cleaning agent.

[0031] Preparation of the above-mentioned wood ash: Waste wood and residues from natural plant materials produced by this patented technology are burned, the ash is collected and crushed. The wood ash is poured into water, stirred, and impurities are filtered out to obtain a wood ash solution.

[0032] Preparation of the above-mentioned zanthoxylum bactericide: 1 kg of dried and pulverized zanthoxylum leaf powder was added to a subcritical treatment device, 15 kg of 90% ethanol aqueous solution was added, the device was sealed, and the reaction was carried out at a temperature of 150℃ and a pressure of 1.5 MPa for 3 hours. The mixture was filtered, the filtrate was collected, and the zanthoxylum bactericide was obtained after concentration.

[0033] The above-mentioned preparation of tea polyphenols: 1 kg of pulverized non-grade green tea powder was added to a subcritical treatment device, 45 kg of distilled water was added, the device was sealed, and the reaction was carried out at 80℃ for 3 h. The mixture was filtered, and the filtrate was cooled to room temperature. After freeze-drying, tea polyphenols were obtained.

[0034] The above-mentioned method for preparing sulfated tea oil is as follows: 1 kg of crushed tea cake powder is added to a subcritical treatment device, 15 kg of 90% ethanol aqueous solution is added, the device is sealed, and the reaction is carried out at a temperature of 150℃ and a pressure of 1.5 MPa for 3 hours. The mixture is then filtered, and the filtrate is cooled to room temperature. 10% NaCl is added, and the mixture is centrifuged. The upper layer is evaporated to dryness to obtain tea oil, which is then subjected to conventional sulfation treatment to obtain a tea oil fatliquoring agent.

[0035] The eco-friendly shoe upper leather prepared by the technical solution of this application was tested, as follows: The above are merely specific embodiments of the present invention, but the design concept of the present invention is not limited thereto. Any non-substantial modifications made to the present invention using this concept shall be considered as infringing upon the protection scope of the present invention.

Claims

1. A method for preparing low cytotoxicity eco-leather based on all natural materials, characterized by: It comprises the following steps: batching → pre-soaking → fleshing and edging → main soaking → fleshing and edging → enzyme unhairing → liming → splitting and edging → deliming → bating → pickling → tara gum-tea polyphenol-zeolite combined tanning → water squeezing, shaving and buffing → rewetting → primary neutralization → fat-liquoring → drying and finishing → finishing; Wherein, Batching: taking wet salted cowhide as rawhide, selecting groups with basically consistent weight, area and color as a group, weighing, and adding 130% weight for metering; Pre-soaking: putting the batched wet salted cowhide into a drum, adding 200% water at 19-21℃, adding 0.2-0.3% tea saponin cleaning agent, 0.2-0.3% penetrating agent, 0.1-0.2% degreasing agent, and 0.3-0.5% wood ash, rotating for 10 min, stopping for 30 min; the rotating speed is 2-3 rpm; the temperature is controlled at 19-21℃, the pH is 6.3-6.7, and the Baume degree is 8-9; repeating 4-6 times; washing with water and discharging from the drum; then fleshing and edging; Main soaking: putting the wet salted cowhide after pre-soaking, fleshing and edging into a drum, adding 200% water at 18-22℃, and rotating at 3 rpm; adding 0.2-0.3% tea saponin cleaning agent, 0.2-0.3% penetrating agent, 0.2-0.3% soaking agent, and 0.2-0.3% degreasing agent, rotating for 10 min, and stopping for 20 min; the pH is 6.3-6.7, and the rotating speed is 2-3 rpm; repeating 1-3 times; adding 0.2-0.4% wood ash and 0.1-0.3% zanthoxylin bactericide, adjusting the pH to 9.5-10.5, rotating for 10 min, and stopping for 20 min; repeating 5-8 times, requiring full penetration and milky white incision; washing with water and discharging from the drum; Enzyme unhairing: putting the wet salted cowhide after main soaking, fleshing and edging into a drum, adding 100% water at 24-28℃, rotating at 6-8 rpm, and adjusting the pH to 9.0-9.5; adding 0.3% penetrating agent, 1.0-1.5% nano negative ion powder, and 0.7-1.3% compound enzyme, rotating for 30 min; adding 0.3-0.5% keratinase, rotating for 30 min; checking the unhairing rate; if the unhairing rate is greater than 90%, entering the next process; otherwise, continuing to rotate for 30-60 min; washing with water, filtering hair, and draining liquid; Liming: putting the cowhide with unhairing rate greater than 90% into a drum, adding 100% water at 24-26℃, rotating at 3-5 rpm; adding 0.3% penetrating agent and 2% lime, rotating for 60 min; adding 100% water at 24-26℃, 50% wood ash solution with a concentration of 20%, and 0.15-0.2% sodium hydroxide solution with a concentration of 30%, rotating for 60 min; then rotating for 5 min, stopping for 55 min, and repeating 5-8 times; washing with water and discharging from the drum; Deliming: putting the cowhide after unhairing and splitting into a drum, adding 50-100% water at 30-35℃, adding 0.3% penetrating agent, and adding 0.7-1.0% non-ammonium organic acid deliming agent, rotating for 15-30 min at 6 rpm; adding 0.7-1.5% non-ammonium organic acid deliming agent, rotating for 15-30 min; adjusting the pH to 8.0-8.5; Softening: continue to add 0.2-0.5% of non-ammonium softening enzyme, 0.3% of degreasing agent, rotate for 10 min, stop for 20 min; adjust temperature to 30-32℃, pH to 7.5-8.5, rotate for 10 min, stop for 20 min; repeat 2-3 times, take incision on the hip, and if the phenolphthalein reagent is colorless, it is considered that the softening is completed; wash with water, and take out the drum; Acid dipping: put the softened cowhide into the drum, add 50-150% of water at 23-25℃, add 7-10% of sodium chloride, rotate for 10 min at 8 rpm; adjust Baume degree to ≥7; add 0.5-1.5% of 85% formic acid diluted with 8-10 times of normal temperature water, rotate for 30 min; add 0.2-0.8% of 98% concentrated sulfuric acid diluted with 8-10 times of normal temperature water, adjust pH to 2.5-3.0, rotate for 60-180 min; control liquid to 50%; then add 10% of 20% wood ash solution, rotate for 30 min; adjust pH to 5.5-6.0; add 4-6% of mirabilite, rotate for 60 min; Tara gum-tea polyphenol-zeolite combined tanning: carried out in the same liquid as acid dipping, add 15-30% of tara gum, 10-20% of tea polyphenol, rotate for 240-480 min, after complete penetration, add 50% of water at 40-50℃, rotate for 60 min; then add 0.1% of formic acid in batches, rotate for 30 min; adjust pH to 3.0-3.5, rotate for 30 min; add 3-5% of zeolite tanning agent auxiliary, rotate for 30-60 min; add 3-5% of zeolite tanning agent, rotate for 30-60 min; add wood ash to adjust pH to 5.4-5.6, rotate for 60-120 min, drain liquid, and take out the drum; Grinding: after water squeezing and uniform cutting, the white wet leather is laid flat, and the sandpaper of the leather grinding machine is used to grind the white wet leather to make the grain surface regular and consistent; Filling: after water squeezing, uniform cutting and grinding, the white wet leather is put into the drum, 80-100% of water, 1% of sodium formate are added, and rotated for 15 min; 10% of 20% wood ash solution is added, pH is adjusted to 5.5-6.5, 3-5% of protein filler and 3-5% of natural dye are added, and rotated for 60-120 min; pH is adjusted to 4.3-4.8 with formic acid, and rotated for 15 min; washed with water; drain water; Fat-liquoring: add 100-150% of water at 45-55℃, 9-18% of sulfated tea oil, 2% of sulfated ox hoof oil, 2% of lecithin fat-liquoring agent, and 4% of natural compound fat-liquoring agent, rotate for 90 min, then adjust pH to 3.6-3.8 with formic acid, rotate for 30 min, soak in 300% glycerol water solution for 24 h, wash with water, and take out the drum.

2. A process for the preparation of low cytotoxicity eco-leather based on all natural materials as claimed in claim 1 wherein: The finishing process is: water squeezing and stretching → vacuum drying → hanging and drying → re-humidification → softening → board drying → backing → polishing → top coating → softening → rolling → sizing and warehousing; the main operation points are as follows: Water squeezing and stretching: carried out on a reciprocating water squeezing and stretching machine, knife distance is 1.10-1.15 mm, water squeezing pressure is 30 bar, and supply speed is 20-25 m / min; after water squeezing, the water content is controlled to 50-55%; Vacuum drying: performed on a vacuum drying machine, drying temperature is 45℃, time is 500s, negative pressure value is 23-26Mbar; moisture content is controlled at 23-30% after vacuum drying; Air drying: performed on a hanging air drying line, air drying time is 24h, moisture content is controlled at 13-18% after air drying; Drying: performed in a constant temperature and humidity drying oven, the temperatures of three ovens are 37℃, 42℃ and 48℃ respectively, humidity is 30-35%, time is 12h, moisture content is controlled at 6-10% after drying; Moisture regain: performed on a moisture regaining machine, moisture content is controlled at 20-25% after moisture regain; Softening: performed in a stainless steel octagonal softening drum, softening drum rotating speed is 15 r / min, time is 6h, the drum rotates forward and backward, the drum temperature is automatically controlled at 25-30℃; moisture content of the crust is 18-20% after softening; Boarding: performed on a horizontal boarding machine, oven temperature is 50℃, boarding distance is 6cm, clamping distance is 10-12cm, the time of the crust passing through the oven is 20min, moisture content of the crust is 14-18%; Sealing: operated on a spraying machine, coating amount is about 5-10g / SF, spraying is performed 1-3 times, each time is 3-5g / sf2, coating amount is about 3-15g / sf2; the coating agent formula is: water 500-1000 parts, water-soluble protein adhesive 500-800 parts, modified protein, modified protein brightener 200-300 parts, penetrant 20-100 parts; bio-based auxiliary agent 50-100 parts; Pressing: performed on a plate ironing machine, plate temperature is 100℃, pressure is 30kg, time is 2s; Top coating: operated on a computer spraying machine, spraying is performed 1-3 times, each time is 2-3g / sf2, coating amount is about 3-5g / sf2; the coating agent formula is: water 100-800 parts, graphene modified organic silicon hand feel agent 10-20 parts, graphene oxide dispersion liquid 10-20 parts; γ-aminopropyl triethoxysilane 50-100 parts; modified protein brightener 200-400 parts; Penetrant 20-100 parts; Bio-based auxiliary agent 50-100 parts; Oscillating softening: operated on an oscillating softening machine, the oscillating softening machine parameters are: conveying speed 9.5m / min, number of stages 5; Rolling: operated on a through-type ironing machine, rolling machine temperature is 120℃, pressure is 20-30kg, speed is 8m / min.

3. A process for the preparation of low cytotoxicity eco-leather based on all natural materials as claimed in claim 1 wherein, Preparation of the tea saponin cleaning agent: 1kg of crushed tea cake powder is added to a subcritical treatment device, 70-90% of an ethanol aqueous solution 10-15kg is added, and then the device is closed and reacted at a temperature of 105-150℃ and a pressure of 0.5-1.5MPa for 0.5-3h, and then filtered, and the filtrate is cooled to room temperature; 0.5-10% of NaCl is added, and then centrifuged, and then the lower layer is evaporated to obtain tea saponin, and then the tea saponin is mixed with wood ash and practical acetic acid to obtain a tea saponin cleaning agent. ​ 4. A process for the preparation of low cytotoxicity eco-leather based on all natural materials as claimed in claim 1 wherein, The preparation of the wood ash: the waste wood and the residue from natural plant material produced by the present technology are burned, the combustion ash is collected, crushed, and the wood ash is poured into water, stirred, and impurities are filtered out, and the wood ash solution is obtained. ​ 5. A process for the preparation of low cytotoxicity eco-leather based on all natural materials as claimed in claim 1 wherein, The preparation of the zanthoxylin bactericide: 1 kg of dried and crushed zanthoxylum leaf powder is added into a subcritical treatment device, 10-15 kg of 70-90% ethanol aqueous solution is added, closed, reacted at a temperature of 105-150 ℃ and a pressure of 0.5-1.5 MPa for 0.5-3 h, filtered, and the filtrate is collected and concentrated to obtain the zanthoxylin bactericide. ​ 6. A process for the preparation of low cytotoxicity eco-leather based on all natural materials as claimed in claim 1 wherein, The preparation of the tea polyphenol: 1 kg of crushed off-grade green tea powder is added into a subcritical treatment device, 15-45 kg of distilled water is added, closed, reacted at a temperature of 60-80 ℃ for 0.5-3 h, filtered, and the filtrate is cooled to room temperature; and the tea polyphenol is obtained after freeze-drying.

7. A process for the preparation of low cytotoxicity eco-leather based on all natural materials as claimed in claim 1 wherein, The preparation method of the sulfated tea oil: 1 kg of crushed tea cake meal powder is added into a subcritical treatment device, 10-15 kg of 70-90% ethanol aqueous solution is added, closed, reacted at a temperature of 105-150 ℃ and a pressure of 0.5-1.5 MPa for 0.5-3 h, filtered, and the filtrate is cooled to room temperature; 0.5-10% NaCl is added, centrifuged, the upper layer is evaporated to dryness to obtain tea oil, and the tea oil is obtained after conventional sulfation treatment. ​

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