CN117071293A - Preparation method of antibacterial and easily dyeable ecologically regenerated genuine leather for household use - Google Patents

Abstract

The invention discloses a preparation method of antibacterial and easily dyeable ecologically regenerated genuine leather for household use, which includes the following steps: S1, preparing a short dermal fiber net; S2, preparing a nylon short fiber net; S3, compounding and spunlace reinforcement: combining the short dermal fibers with The net is compounded on top of the nylon short fiber net, pre-wetted and then spunlace reinforced, dehydrated and dried to obtain a spunlace non-woven fabric; S4, impregnated and adhered to the microfiber base: the spunlace non-woven fabric is ironed and hot-melt adhesive mesh is used Membrane: The spunlace non-woven fabric and the superfine fiber Bess are pressed and laminated together, and then cooled to obtain a composite non-woven fabric; S5, dyeing: the composite non-woven fabric is immersed in the impregnation liquid for dyeing, and dried to obtain a leather base material; S6, surface Dry veneer: Coat the surface layer slurry on the release paper, dry it, apply the adhesive layer slurry on the surface of the surface layer, semi-dryly attach it to the leather base material, mature, cool and peel off the release paper. That’s ecologically regenerated real leather. The preparation method of the invention has renewable and environmentally friendly raw materials, can effectively reduce the use of fossil-based raw materials and reduce carbon emissions.

Description

Preparation method of antibacterial and easily dyeable ecologically regenerated genuine leather for household use

Technical field

The invention belongs to the technical field of synthetic leather, and particularly relates to a preparation method of household antibacterial and easily dyeable ecologically regenerated genuine leather.

Background technique

my country is the world's largest leather producer and consumer. A large amount of leather scraps are produced during the leather production process, such as shaved dander from tanneries, animal leather scraps, and trimmed leather pieces from shoe factories. At the same time, Abandoned leather consumables will also be accompanied by a large amount of leather waste. If these leather wastes are directly discarded into the environment without treatment, they will cause harm to the environment. Currently, leather waste is mostly processed through recycling, landfilling, and incineration. Only a small part of high-quality leather has the value of recycling, and most of the waste materials that are difficult to be recycled and reused are mostly disposed of by landfill and incineration. Landfilled leather waste is difficult to decompose and takes up a lot of land. The incineration process Some pollutants will be produced, which may easily cause secondary pollution to the environment. If the leather fibers in leather waste can be recycled and fully utilized, resource waste can be greatly reduced and the environment can be protected. The present invention is conducted based on this purpose.

Contents of the invention

The invention provides a preparation method for household antibacterial and easily dyeable ecologically regenerated real leather. The source of raw materials is renewable, and all links of the entire supply chain can achieve closed-loop environmental protection of recyclability and recyclability, thereby maximizing resource conservation. , effectively reducing the use of fossil-based raw materials such as petroleum and reducing carbon emissions.

In order to achieve the above objects, the present invention adopts the following technical solutions:

The invention provides a preparation method for household antibacterial and easily dyeable ecologically regenerated real leather, which includes the following steps:

S1, preparation of short dermal fiber mesh;

S2, prepare nylon short fiber mesh;

S3, compounding and spunlace reinforcement, the specific process is: compound the leather short fiber web produced in S1 online on top of the nylon short fiber web produced in S2, pre-wet it and enter the spunlace area for spunlace reinforcement and dehydration Drying to obtain spunlace non-woven fabric;

S4, impregnating and laminating microfiber bass, the specific process is: the spunlace non-woven fabric produced in S3 is ironed at 115-135°C, and a hot melt adhesive film is used to combine the spunlace non-woven fabric with The microfiber Bess heat press is pressed and laminated, then cooled to obtain a composite non-woven fabric;

S5, dyeing, the specific process is: immerse the composite non-woven fabric prepared in S4 into the impregnation liquid for impregnation dyeing, and dry it at 60-80°C for 8-12 hours to obtain a leather base material;

S6, surface dry veneer treatment, the specific process is: apply the surface layer slurry on the release paper, dry it, and evenly apply the adhesive layer slurry on the surface of the surface layer, and combine it with the leather prepared in S5 The base material is semi-dryly laminated, cured at 130-140°C for 10-15 minutes, and the release paper is peeled off after cooling to obtain the ecologically regenerated genuine leather.

In the above technical solution, in S1, the specific process of preparing the dermal short fiber web is:

S11, clean and remove animal leather scraps and scraps, dry them and crush them using a leather grinder;

S12, crush and wash with alkali, adjust the pH to 7, and obtain dermal short fibers;

S13, through air-laying, opening and carding into single fibers, under the combined action of the centrifugal force of the cylinder's high-speed rotation and the airflow, the fibers are transported and gathered on the web-forming curtain by the airflow to obtain the dermal short fiber web.

In the above technical solution, in S2, the specific process of preparing nylon short fiber web is:

S21, renewable plant raw materials undergo biological fermentation, purification, polymerization and melt spinning to obtain primary fibers;

S22, the nascent fiber is sequentially oiled, drawn, crimped, dried, and cut to obtain nylon short fiber with a length of 50-60mm and a fineness of 6-7 denier;

S23, the nylon short fiber is carded into a web, and after opening and carding, it is condensed and output by the doffer to form a fiber web, and the nylon short fiber web is obtained.

In the above technical solution, in S5, the impregnation liquid is made of the following components by weight: 100 parts of water-based polyurethane resin, 0.5-5 parts of dispersant, 0.1-1 part of viscosity stabilizer, 1-1 part of flame retardant 10 parts, 0.1-1 part of antibacterial agent, 15-30 parts of filler and 1-10 parts of cellulose-based polymer color paste powder.

In the above technical solution, the preparation method of the cellulose-based polymer color paste powder includes the following steps:

Step (1), prepare lignin-cellulose acetate nanofiber membrane by electrospinning. The specific process is:

Dissolve lignin and cellulose acetate in acetic acid-tetrahydrofuran, acetic acid or acetic acid-acetone solution to prepare a 15-30wt% spinning solution. The spinning distance is 10-15cm, the voltage is 20-35KV, and the flow rate is 0.1-1mL/h. Obtain nanofiber membrane;

Step (2): Add the nanofiber membrane and reactive dye to the solvent system according to a certain liquor ratio, dye it in the range of 80-100°C for 2-3 hours, lower it to room temperature, and then dye the dyed nanofiber membrane. After washing with soap and water and freeze-drying, the cellulose-based polymer color paste powder is obtained.

In the above technical solution, in step (2), the reactive dye is one of reactive blue 19 dye, reactive red 194 dye, and reactive yellow 145 dye, the dosage of reactive dye is 50-300o.w.f%, and the liquor ratio is 1:10-1:30.

In the above technical solution, in step (2), the solvent system is dimethyl sulfoxide-ethyl n-octanoate, dimethyl sulfoxide-dimethylformamide, dimethyl sulfoxide-dimethyl carbonate one of them.

In the above technical solution, in S6, the surface layer slurry is made by mixing the following components by weight: 100 parts of resin, 0.1-1 part of leveling agent, 0.1-0.5 part of defoaming agent, 5 parts of filler -30 parts, 1-10 parts of wear-resistant agent, 0.1-5 parts of light stabilizer, 0.1-10 parts of anti-hydrolysis agent and 1-10 parts of colorants.

In the above technical solution, in S6, the adhesive layer slurry is made by mixing the following components by weight: 100 parts of resin, 0.1-1 part of catalyst, 0.01-1 part of inhibitor, and cross-linking agent 2 -10 parts, 5-30 parts of filler.

The beneficial effects of the present invention are:

1. The preparation method of the present invention superimposes a nylon short fiber web and a leather short fiber web, and hydroentangles them to obtain a non-woven fabric, which is then bonded with ultrafine fiber bass to serve as a recycled leather base material for furniture. Nylon staple fiber has excellent flame retardancy, easy dyeing at low temperature, soft and skin-friendly, easy to absorb and discharge, weather-resistant and wear-resistant. The source of raw materials is renewable, and all links of the entire supply chain can be recycled and reused. Closed-loop environmental protection, thereby maximizing resource conservation, effectively reducing the use of fossil-based raw materials such as petroleum, and reducing carbon emissions.

2. The impregnation and veneer processes in the preparation method of the present invention use water-based polyurethane, which is environmentally friendly. The color paste used is cellulose-based polymer color paste powder, which is sustainable and will not pollute the environment. Moreover, the preparation of cellulose-based high-quality The molecular color paste is dyed using a solvent system. The solvent can be recycled and dyed directly during the preparation of ultrafine fiber synthetic leather, thus reducing the secondary dyeing process of ultrafine fiber synthetic leather in the later stage.

Detailed ways

In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below with reference to specific embodiments. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the invention will be limited only by the claims.

The invention provides a preparation method for household antibacterial and easily dyeable ecologically regenerated real leather, which includes the following steps:

1. Preparation of dermal short fiber mesh. The specific process is:

1. Clean and remove animal leather scraps and scraps, dry them and crush them using a leather grinder;

2. After crushing, wash with alkali and adjust the pH to 7 to obtain short dermal fibers;

3. Single fibers are formed by air-laying, opening and carding. Under the combined action of the centrifugal force of the cylinder's high-speed rotation and the airflow, the fibers are transported by the airflow and gathered on the web-forming curtain to obtain a short leather fiber web.

Among them, the alkali solution used in alkali washing is a combination of various weak alkalis, such as sodium bicarbonate, sodium silicate, aminophylline, alum, etc., which can react with the fat and protein in animal leather to form water-soluble substances, making the The animal leather scraps are decomposed and the fur is separated. The mass ratio of the animal leather scraps and scraps to the compound alkali solution is 1:15-20. After treatment at 60-80°C for 2-4 hours, the pH is adjusted to 7. As one of the examples, the alkali solution is made by mixing the following components by weight: 20-30 parts of sodium bicarbonate, 5-10 parts of ethylenediamine, 3-5 parts of sodium silicate, 1-3 parts Aminophylline, 1-3 parts alum and 30-40 parts water.

The length of short dermal fibers is less than 80mm, and the mass of the fiber web per unit area is 100-1000g/m ² . The diameter of the cylinder is 400-600mm, the rotation speed is 1700-2000r/min, and the output speed is 0.5-50m/min.

2. Preparation of nylon short fiber mesh:

1. Renewable plant-based raw materials undergo biological fermentation, purification, polymerization and melt spinning to obtain primary fibers. Renewable plant-based raw materials include crops and their wastes, such as corn stalks, grain starch, etc.;

2. The virgin fiber is oiled, drawn, crimped, dried and cut in sequence to obtain nylon short fiber with a length of 50-60mm and a fineness of 6-7 denier;

3. The nylon short fibers are carded into a web. After opening and carding, they are condensed and output by the doffer to form a fiber web. Through parallel series stacking, the network can be superimposed to a certain quality and thickness. As one of the embodiments, the thickness of the nylon short fiber parallel series stacked web is 0.5-1mm.

3. Composite and spunlace reinforcement

The leather short fiber net is compounded online on top of the nylon short fiber net, and after pre-wetting, it enters the spunlace area for spunlace reinforcement, and is dehydrated and dried to obtain a spunlace non-woven fabric, which is cut and ready for use.

The thickness of leather-nylon composite non-woven fabric is 1.5-2mm, and the weight is 500-1500g/m ² . The water needle pressure is 5*10 ⁶ Pa-1*10 ⁷ Pa.

4. Impregnated and bonded microfiber bass

The spunlace non-woven fabric is ironed at 115-135°C, and the hot-melt adhesive film is used to press and laminate the spunlace non-woven fabric and the microfiber Bess heat press, and then cool and set aside.

Among them, the hot melt adhesive film used can be PA hot melt adhesive film, SWA120, XWA116, etc., or TPU hot melt adhesive film, GXJU150, HJU120, etc. The pressing temperature is 140-160℃, the pressing time is 10-15s, and the pressing pressure is 1.5-2.5Kgf/m ² .

5. Dyeing

The composite non-woven fabric adhered to the superfine fiber bass is immersed in the impregnation liquid (water-based polyurethane containing cellulose-based polymer color paste powder) for impregnation dyeing, and dried at 60-80°C for 8-12 hours to obtain a leather base material .

The formula of the impregnation liquid used is as follows:

Among them, the preparation method of cellulose-based polymer color paste powder is as follows:

1. Preparation of lignin-cellulose acetate nanofiber membrane by electrospinning

Dissolve lignin and cellulose acetate in acetic acid-tetrahydrofuran, acetic acid or acetic acid-acetone solution to prepare a spinning solution with a mass fraction of 15-30%. The spinning distance is 10-15cm, the voltage is 20-35KV, and the flow rate is 0.1-1mL/h.

2. Add the cellulose film and reactive dye to the solvent system according to a certain liquor ratio, dye it at 80-100°C for 2-3 hours, and lower it to room temperature. Then, the dyed cellulose is washed with soap and water and freeze-dried for 24 hours. Finally, cellulose-based polymer color paste powder is obtained.

The dosage of reactive dye is 50-300% (o.w.f), and the liquor ratio is 1:10-1:30.

Reactive dye is one of reactive blue 19 dye, reactive red 194 dye, and reactive yellow 145 dye.

The solvent system is one of dimethyl sulfoxide-ethyl n-octanoate, dimethyl sulfoxide-dimethylformamide, and dimethyl sulfoxide-dimethyl carbonate.

6. Surface dry veneer treatment

Apply the surface layer slurry on the release paper and dry it;

The adhesive layer slurry is evenly applied on the surface of the surface layer and semi-dryly adhered to the leather base material. Curing at 130-140℃ for 10-15 minutes, cooling and peeling off the release paper. Different patterns of the release paper will produce leather with different styles and patterns.

The formula for dry veneers is shown in the table below:

The preparation method of the present invention is used to prepare antibacterial and easily dyeable ecologically regenerated genuine leather for home use, and the finished product is subjected to performance testing. The test results are as shown in the table below.

Test items Test Results Folding resistance ≥50000 times Wear resistance ≥1000 rpm Tear load ≥20 Stain resistant No oil shrinkage when writing, wipe with dry cloth, leaving no traces Resistant to hydrolysis better Tensile load N/3cm ≥250 Peeling load N/3cm ≥100 UV resistant/UV resistant ≥Level 3 Flame retardancy ≤100mm/min VOC Single substance <1ug/m ³ , total content <5ug/m ³ softness ≥5 Breathability ≥150ml/ ^cm2 ·h

Obviously, the above-mentioned embodiments are only examples for clear explanation and are not intended to limit the implementation. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. An exhaustive list of all implementations is neither necessary nor possible. The obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims (9)

1. The preparation method of the household antibacterial easy-dyeing ecological regenerated real leather is characterized by comprising the following steps of: the method comprises the following steps:

s1, preparing a dermis short fiber net;

s2, preparing a nylon short fiber net;

s3, compounding and water jet reinforcement, wherein the concrete process is as follows: compounding the dermis short fiber web prepared in the step S1 above the nylon short fiber web prepared in the step S2 on line, pre-wetting, then entering a hydro-entangled area for hydro-entangled reinforcement, dehydrating and drying to obtain a hydro-entangled non-woven fabric;

s4, impregnating and attaching superfine fiber bass, wherein the specific process is as follows: ironing the spun-laced non-woven fabric prepared in the step S3 at 115-135 ℃, ironing and attaching the spun-laced non-woven fabric and a superfine fiber bass hot press by using a hot melt adhesive net film, and cooling to obtain a composite non-woven fabric;

s5, dyeing, wherein the specific process is as follows: immersing the composite non-woven fabric prepared in the step S4 into an immersion liquid for immersion dyeing, and drying at 60-80 ℃ for 8-12 hours to obtain a leather substrate;

s6, surface dry veneering treatment, which comprises the following specific processes: coating the surface layer slurry on release paper, drying, uniformly coating the adhesive layer slurry on the surface of the surface layer, semi-drying and attaching the surface layer slurry to the leather base material prepared in the step S5, curing for 10-15min at 130-140 ℃, cooling and stripping the release paper to obtain the ecological regenerated real leather.

2. The method of manufacture of claim 1, wherein: in S1, the specific process for preparing the dermis short fiber web is as follows:

s11, cleaning and removing impurities from animal leather scraps and scraps, and crushing the animal leather scraps and scraps by using a leather crusher after drying;

s12, crushing, alkali washing, and regulating the pH value to 7 to obtain the dermis short fiber;

s13, opening and carding into single fibers through air-laying, and gathering the fibers on a web-forming curtain by air-conveying under the combined action of the centrifugal force of high-speed rotation of a cylinder and the air-conveying, so as to obtain the dermis short fiber web.

3. The method of manufacture of claim 1, wherein: s2, preparing a nylon short fiber net by the following specific processes:

s21, performing biological fermentation and purification on renewable plant raw materials, and performing melt spinning after polymerization to obtain nascent fibers;

s22, oiling, drafting, curling, drying and cutting the nascent fiber in sequence to obtain nylon short fiber with the length of 50-60mm and the fineness of 6-7 denier;

s23, carding the nylon short fibers into a net, opening, carding, condensing by doffer and outputting to form a fiber net, so as to obtain the nylon short fiber net.

4. The method of manufacture of claim 1, wherein: s5, preparing the impregnation liquid by the following components in parts by weight: 100 parts of aqueous polyurethane resin, 0.5-5 parts of dispersing agent, 0.1-1 part of viscosity stabilizer, 1-10 parts of flame retardant, 0.1-1 part of antibacterial agent, 15-30 parts of filler and 1-10 parts of cellulose-based polymer color paste powder.

5. The method of claim 4, wherein: the preparation method of the cellulose-based polymer color paste powder comprises the following steps:

step (1), preparing a lignin-cellulose acetate nanofiber membrane by electrostatic spinning, wherein the specific process comprises the following steps:

dissolving lignin and cellulose acetate in acetic acid-tetrahydrofuran, acetic acid or acetic acid-acetone solution, preparing spinning solution with 15-30wt% and spinning distance of 10-15cm, voltage of 20-35KV and flow rate of 0.1-1mL/h, and preparing nanofiber membrane;

and (2) adding the nanofiber membrane and the reactive dye into a solvent system according to a certain bath ratio, dyeing for 2-3 hours at the temperature of 80-100 ℃, cooling to room temperature, washing the dyed nanofiber membrane with soaping water, and freeze-drying to obtain the cellulose-based polymer color paste powder.

6. The method of manufacturing according to claim 5, wherein: in the step (2), the reactive dye is one of reactive blue 19 dye, reactive red 194 dye and reactive yellow 145 dye, the dosage of the reactive dye is 50-300o.w.f%, and the bath ratio is 1:10-1:30.

7. The method of manufacturing according to claim 5, wherein: in the step (2), the solvent system is one of dimethyl sulfoxide-ethyl n-octoate, dimethyl sulfoxide-dimethylformamide and dimethyl sulfoxide-dimethyl carbonate.

8. The method of manufacture of claim 1, wherein: in S6, the surface layer slurry is prepared by mixing the following components in parts by weight: 100 parts of resin, 0.1-1 part of flatting agent, 0.1-0.5 part of defoamer, 5-30 parts of filler, 1-10 parts of wear-resistant agent, 0.1-5 parts of light stabilizer, 0.1-10 parts of hydrolysis-resistant agent and 1-10 parts of pigment.

9. The method of manufacture of claim 1, wherein: s6, the adhesive layer slurry is prepared by mixing the following components in parts by weight: 100 parts of resin, 0.1-1 part of catalyst, 0.01-1 part of inhibitor, 2-10 parts of cross-linking agent and 5-30 parts of filler.