CN116905243A - Bio-based bamboo fiber synthetic leather and preparation method thereof - Google Patents
Bio-based bamboo fiber synthetic leather and preparation method thereof Download PDFInfo
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- CN116905243A CN116905243A CN202310689639.4A CN202310689639A CN116905243A CN 116905243 A CN116905243 A CN 116905243A CN 202310689639 A CN202310689639 A CN 202310689639A CN 116905243 A CN116905243 A CN 116905243A
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- 241000191967 Staphylococcus aureus Species 0.000 description 2
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/12—Permeability or impermeability properties
- D06N2209/121—Permeability to gases, adsorption
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1635—Elasticity
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The application discloses a biological-based bamboo fiber synthetic leather and a preparation method thereof, wherein the method comprises the following steps: taking 100% bamboo fiber non-woven fabric as a substrate; sequentially carrying out impregnation material rolling, pre-solidifying, coating fabric, solidifying to obtain a semi-finished product, wherein the impregnation material adopts fluorine-free bio-based high-modulus impregnation resin, the coating process adopts bio-based polyester polyether blending resin, and cellulose is added to adjust the hardness; and washing the solidified semi-finished product with water, and heating and drying to obtain the bio-based bamboo fiber synthetic leather. The application takes 100% bamboo fiber non-woven fabric as a substrate, and selects bio-based polyurethane resin for matching, and the softness and hardness are adjusted by adding cellulose in the formula. The biological base synthetic leather with the performances of moisture absorption, ventilation, antibiosis, bacteriostasis and the like is developed by combining the wet process flow with the bamboo fiber non-woven fabric, can be widely used for the inner leather of the case and the bag, and has the biological base content of more than 60 percent, thereby being environment-friendly.
Description
[ field of technology ]
The application relates to the technical field of synthetic leather, in particular to biological-based bamboo fiber synthetic leather and a preparation method thereof.
[ background Art ]
As fossil resources are increasingly exhausted, the massive consumption of fossil resources has led to environmental pollution and energy crisis. The search for renewable raw materials to replace traditional raw materials is an urgent requirement for the development of polyurethane material technology. Polyurethane paint has been widely used in the fields of national defense, aerospace, clothing leather, shoe leather and the like because of its excellent adhesive force, weather resistance, chemical corrosion resistance and decoration. The conventional polyurethane material is derived from petrochemical products, and thus has a harmful effect on the environment during the production, use and disposal thereof.
The bio-based material is a new material prepared by taking renewable resources as raw materials and adopting physical, chemical or biological methods. It has the advantages of renewable raw materials, biodegradability, environmental friendliness and the like. The biological base material is adopted to replace or partially replace petrochemical products to prepare the polyurethane coating, so that the energy crisis can be relieved, the environmental pollution is reduced, the requirement of current sustainable development is met, and the polyurethane coating is becoming one of the important directions of polyurethane coating development.
The bamboo fiber is novel ecological environment-friendly regenerated cellulose fiber, is called as breathing fiber, and the bamboo fiber non-woven fabric has the advantages of good biodegradability, deodorization and adsorption, antibiosis and bacteriostasis, ultraviolet resistance, natural health care, lubrication, fineness, good drapability, good hygroscopicity, good air permeability and the like.
[ application ]
The application aims to overcome the defects of the prior art and provides a preparation method of a more environment-friendly bio-based bamboo fiber synthetic leather.
In order to solve the above-mentioned purpose, the application adopts the technical scheme that:
the preparation method of the bio-based bamboo fiber synthetic leather is characterized by comprising the following steps of:
taking 100% bamboo fiber non-woven fabric as a substrate;
sequentially carrying out impregnation material rolling, pre-solidifying, coating fabric, solidifying to obtain a semi-finished product, wherein the impregnation material adopts fluorine-free bio-based high-modulus impregnation resin, the coating process adopts bio-based polyester polyether blending resin, and cellulose is added to adjust the hardness;
and washing the solidified semi-finished product with water, and heating and drying to obtain the bio-based bamboo fiber synthetic leather.
Preferably, the non-woven fabric substrate is prepared by needling a double-layer composite 100% bamboo fiber spunlaced non-woven fabric and then performing hot roller rolling shaping.
Preferably, the impregnating material is prepared by stirring and mixing fluorine-free bio-based high-modulus impregnating resin, a tearing-resistant auxiliary agent, a moisture absorption antibacterial auxiliary agent, a leveling agent and a first solvent; the biobased content of the fluorine-free biobased high-modulus impregnating resin is more than 40%, and the room temperature viscosity of the impregnating material is controlled between 200 and 260cps.
Preferably, the method comprises: the sizing agent of the coating fabric is fluorine-free and is obtained by stirring and mixing bio-based polyester polyether blend resin, cellulose, a surfactant and a second solvent; the mixed slurry is stirred for 30-35 minutes at the stirring speed of 1000-1500r/min at normal temperature.
Preferably, in the process of coating the facing with the slurry, the weight ratio of the polyester polyether blend resin to the cellulose is 100:20, wherein the slurry has a room temperature viscosity of 12000-15000cps.
Preferably, the first solvent and the second solvent are both N, N-dimethylformamide; the color paste is added into the impregnating material and/or the coating slurry.
Preferably, the solidification in the solidification tank adopts a three-layer solidification mode, and the trolley speed is 9-10m/min.
Preferably, the thickness of the solidified semi-finished product is controlled to be between 1.25 and 1.30 mm; the washing device is provided with a plurality of groups of washing tanks, wherein the temperature of the final washing is controlled to be 70-80 ℃.
Preferably, the heat drying includes: the hot roller is pre-heated at 100-120 ℃, and then dried at 145-165 ℃.
The application further aims to overcome the defects of the prior art and provide the green and environment-friendly bio-based bamboo fiber synthetic leather.
In order to solve the above-mentioned purpose, the application adopts the technical scheme that:
the thickness of the bio-based bamboo fiber synthetic leather prepared by the preparation method of the bio-based bamboo fiber synthetic leather is 1.18-1.23mm, and the softness test value is 1.8-2.2.
After the scheme is adopted, the bio-based bamboo fiber synthetic leather and the preparation method thereof adopt bio-based hydrolysis-resistant high-stripping wet polyether polyester blending polyurethane resin, the resin takes polylactic acid-polyethylene glycol copolymer (PLEG) synthesized by taking racemic lactic acid (D, L-LA) and polyethylene glycol (PEG) as raw materials as a soft segment, isophorone diisocyanate (IPDI) as a hard segment, dibutyl tin dilaurate as a catalyst to prepare a prepolymer, and then the bio-based 1, 4-Butanediol (BDO) is utilized for chain extension. The polyurethane resin has physical indexes of 32% -34% of solid content, 7.0-9.0Mpa of modulus, more than 30MPa of breaking strength, 25-30 ten thousand CPS/25 ℃ of viscosity range and more than 40% of biological base content; compared with the common resin, the resin adopts renewable bio-based raw materials to replace petroleum-based raw materials, is renewable, can be recycled, has more excellent biodegradability and is more environment-friendly. The resin does not contain fluorine compounds, and has the advantages of excellent finished leather rebound resilience, stiff hand feeling and the like. The impregnating resin is bio-based high-modulus polyurethane resin, the solid content of the resin is 29-31%, the modulus is 17-21MPa, the breaking strength is more than 45MPa, the elongation is more than or equal to 200%, and the viscosity range is 18-28 kiloCPS/25 ℃. The resin has the biological base content of more than 40%, good myogenic property, high hardness and smooth surface.
[ description of the drawings ]
Fig. 1 is a schematic flow chart of a production device according to an embodiment of the application.
[ detailed description ] of the application
The following description of the embodiments of the present application will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The application provides a preparation method of bio-based bamboo fiber synthetic leather, which comprises the following steps:
taking a double-layer 100% bamboo fiber non-woven fabric which is subjected to needling shaping and reinforcement as a substrate;
rolling the non-woven fabric substrate by using impregnation materials which are fluorine-free and adopt bio-based high-modulus impregnation resin;
pre-solidifying the impregnated material after rolling;
coating fabric after pre-solidification, wherein bio-based polyester polyether blending resin is selected in the coating process, and cellulose is added to adjust the hardness;
solidifying in a solidification tank to obtain a semi-finished product;
and washing the solidified semi-finished product with water, and heating and drying to obtain the bio-based bamboo fiber synthetic leather.
The process method can produce the environment-friendly synthetic leather which is moisture-absorbing, breathable, antibacterial and bacteriostatic and contains more than 60% of biological base.
Referring to fig. 1, in the embodiment of the application, a double-layer composite base fabric prepared by needling and shaping a commercially available 100% bamboo fiber non-woven fabric is used as a base, and the bamboo fiber non-woven fabric has antibacterial, bacteriostatic and bactericidal effects. When observed under a microscope, bacteria can be greatly propagated in fiber products such as cotton, wood and the like, but bacteria on the bamboo fiber non-woven fabric can not only survive for a long time, but also disappear or reduce in a short time, and the bacterial death rate reaches more than 75% within 24 hours. The new discovery of Japanese authorities increases the added value of the product, and the results are also confirmed by detection of China cotton textile product quality supervision and inspection center and China academy of sciences Shanghai microbiological institute. The cotton product itself does not have the functions of antibiosis and bacteriostasis, and the results of mildew, off-flavor and stickiness are the result of mass propagation of bacteria on the cotton product. The bamboo fiber non-woven fabric does not have the phenomenon, mainly because the bamboo fiber non-woven fabric has the antibacterial and bacteriostatic functions, and bacteria cannot reproduce on the bamboo fiber non-woven fabric, and even cannot survive. The bamboo fiber non-woven fabric is not mildewed, smell-changed and sticky even in a warm and moist environment. The bamboo fiber non-woven fabric also has strong ultraviolet resistance. As proved by the detection of Shanghai physical research institute of China academy of sciences, the transmittance of cotton is 25% for ultraviolet rays with the wavelength of 200-400 nm, the transmittance of bamboo fiber is less than 0.6%, and the ultraviolet resistance of the cotton is 41.7 times of that of cotton.
The resin used for the impregnation material in the embodiment of the application is bio-based high-modulus resin, the solid content is 29-31%, the modulus is 17-21MPa, the breaking strength is more than 45MPa, the elongation is more than or equal to 200%, and the viscosity range is 18-28 kiloCPS/25 ℃. The resin has good myogenic property, high hardness and smooth surface.
In a preferred embodiment of the present application, the impregnation material is obtained by stirring and mixing a bio-based high modulus impregnation resin and a first solvent; the first solvent is preferably N, N-Dimethylformamide (DMF). The impregnating material can also comprise a tearing-resistant additive, a nonionic surfactant, a leveling agent, a hygroscopic bacteriostasis additive and the like, and the tearing-resistant additive XCW-08WH (purchased from Asahi chemical Co., ltd.) can improve the tearing resistance. The nonionic surfactant S-7 (purchased from Shanghai polymer materials Co., ltd.) preferably contains polyether and silicone oil as main components, does not contain fluoride ions, and has certain effect on adjusting cells and hand feeling. The main component of the leveling agent HS-1868 (purchased from Minglong chemical Co., ltd.) is organic silicon, and the leveling agent HS-1868 is added into the impregnating material, so that the dispersibility of the color paste can be improved, and the mottle can be prevented. The moisture absorption and bacteriostasis auxiliary agent (Shanghai tile plus biotechnology Co., ltd.) can improve the moisture absorption and air permeability and improve the hand feeling.
When the preferred embodiment of the present application is specifically configured, the impregnating resin: n, N-dimethylformamide: leveling agent: tear resistance aids: nonionic surfactant: the moisture absorption and bacteriostasis auxiliary agent is prepared from the following components in percentage by weight: 150-200:0.5-2.0:14-16:0.5-2.0:0.5 to 2.0 weight percent. The impregnating resin with the proportion has higher solidification speed, and the foam holes are larger, so that the problem of hand feeling is solved by adjusting the viscosity of the impregnating material. Through different test comparison, when the added parts of N, N-dimethylformamide are 150-200 parts, the softness of hand feeling can meet the requirements. Preferably, the main material mixed soaking liquid is stirred at the stirring speed of 1000-1500r/min at normal temperature for 15-20 min until the resin and the auxiliary agent are completely dissolved, and the room temperature viscosity is controlled at 200-260cps.
In the embodiment of the application, 100% of the bamboo fiber non-woven fabric is subjected to needling reinforcement through a needling machine and then is subjected to hot roller rolling shaping (the temperature of the hot roller is controlled to be 60-70 ℃) to prepare the double-layer composite bamboo fiber non-woven fabric.
And unreeling the double-layer bamboo fiber non-woven fabric substrate, and then carrying out impregnation material rolling (impregnation for short), namely, putting the bamboo fiber non-woven fabric through a cloth storage frame, controlling the speed of the vehicle to be 9-10m/min, and controlling the pressure of an impregnation oil pressing rod to be 5.0-5.5Kg through an impregnation tank with impregnation material. The impregnated fabric is subjected to a pre-solidification tank, the sugar degree of the pre-solidification tank is controlled to be 28-32% (the sugar degree is the DMF concentration in DMF aqueous solution, the sugar degree is obtained by measuring data obtained by an Abbe refractometer, the pressure of a pre-solidification oil pressure roller is also controlled to be 5.0-5.5Kg, and the base fabric is ironed by a six-round ironing device (the ironing temperature is controlled to be 50-60 ℃).
For the selection of polyurethane resin in the coating process, the bio-based polyester polyether blend type resin is selected in the embodiment of the application, and the bio-based polyester polyether blend type resin is generally high in solid content, excellent in leather-forming rebound resilience and free of fluorine compounds. Specifically, the solid content is preferably 32-34%, the percentage modulus is 21-25MPa, the breaking strength is more than 55MPa, the elongation is more than or equal to 250%, and the viscosity is 18-28 kiloCPS/25 ℃. The resin has fine cells, good myogenic property, high hardness and smooth surface, and the finished product is stiffer.
The proportion of the fabric additive in the embodiment of the application is that the polyester polyether blend type resin: n, N-dimethylformamide: hydrolysis resistance auxiliary agent: surfactant 1 to surfactant 2 to filler is added in a weight ratio of 100:50:0.5:1:1.5:20, wherein surfactant 1 can enlarge cells. The surfactant 2 can make the cells more uniform, enhance the DMF-water replacement speed and improve the water washing effect. The hydrolysis resistance auxiliary agent is added into the fabric, so that the integral hydrolysis resistance can be improved. The size of the foam holes is improved by adding cellulose as a filler in the formula, and meanwhile, the finished product can be endowed with good hand feeling. Through adding different parts of cellulose, the addition amount of 18-23 parts, preferably 20 parts, is finally determined, and the requirements can be met.
Further, the mixed fabric is stirred at a high speed of 1000-1500r/min at normal temperature for 30-35 minutes until the polyurethane, the filler and the hydrolysis-resistant auxiliary agent are completely dissolved, the time of stirring the fabric at the high speed is strictly controlled between 30-35 minutes, the too short time of slurry is likely to be insufficient in stirring, and the too high temperature of the material can cause dead material. Stirring until the slurry is uniform, reducing the stirring speed to 300+/-50 r/min, and vacuum defoaming for 90min, wherein the viscosity can be controlled between 12000cps and 15000cps (the temperature is 35 ℃).
In the process of coating slurry, the thickness of the coating can be controlled by adjusting the clearance of a scraper, the clearance of the coating is controlled to be 1.9-2.0mm, and the coating weight is controlled to be 1.1+/-0.05 kg/y. After the doctor blade coating is finished, the surface condition of the coating is observed, and the coating is treated abnormally and timely.
After finishing coating, the solidification in the single-layer solidification tank is performed at a speed which is too high, so that the cells are larger, stripping is affected, the solidification in the solidification tank is preferably performed in a three-layer solidification mode, and the speed of the machine trolley is 9-10m/min. In the preferred embodiment of the application, the coated fabric layer enters a three-fold solidification tank (shown in figure 1) with the length of 30m, is solidified in the solidification tank for a long time, water is used for replacing DMF to realize foaming of the wet-process coating, the solidification sugar degree can be 18-23%, and the temperature is controlled at 28-33 ℃. According to the embodiment of the application, the solidification time of the solidification tank is increased by the solidification of the three-fold solidification tank, so that the slurry is solidified more fully, and the cells are finer, thus the combination treatment of the coating cells, the formula and the production process is integrated, and the produced product meets the requirements of physical properties, hand feeling and the like.
After the synthetic leather semi-finished product obtained by the embodiment of the application is discharged from the coagulation tank, the surface condition is observed, the thickness and the width are measured, the thickness is preferably controlled to be 1.25-1.30mm, and the width is preferably controlled to be 1.43-1.46m. Then, the water enters a plurality of groups of washing tanks to wash DMF in the base cloth; generally, 15 groups of water washing tanks are arranged, the water washing sugar degree of the first six groups is controlled to be 10-20%, the water washing sugar degree of the middle six groups is controlled to be 0-10%, wherein the water washing sugar degree of the last three groups is 0%, and the water temperature is controlled to be 70-80 ℃.
In a specific embodiment of the present application, the bass after the water outlet washing tank is heated and dried, preferably comprising: pre-ironing by eight ironing rolls, wherein the temperature is controlled to be 110-120 ℃; the pre-scalded bass is dried by a baking oven, and the temperature of the baking oven sequentially passes through is as follows: the first group of ovens has a temperature of 150 ℃, the second to fourth groups of ovens has a temperature of 160 ℃, and the fifth group of ovens has a temperature of 140 ℃ until complete drying. After drying, the leather can be cooled and rolled, the thickness of the synthetic leather product is 1.18-1.23mm, and the breadth is 1.43-1.46m.
According to the implementation steps, the embodiment of the application can be used for manufacturing the bio-based bamboo fiber synthetic leather in a consistent operation mode. The produced bass finished product is tested to be peeled off in three centimeters, and can reach 50N/3cm; the softness test value is between 1.8 and 2.2, the fluorine content meets the environmental protection requirement, and the product also has the functions of moisture absorption, ventilation, antibiosis and bacteriostasis, and the biobased content is above 60%.
Calculating the bio-based content: the gram weight of the double-layer bamboo fiber spunlaced non-woven fabric is 160 g/square meter, the gram weight of a sample is 240 g/square meter when the fabric is not coated by doctor-blade impregnation, the gram weight of the impregnation is 80 g/square meter, the gram weight of the sample is 500 g/square meter when the fabric is also coated by doctor-blade impregnation, the gram weight of the fabric is 260 g/square meter, the biological base component gram weight in the impregnation is about 30 g/square meter, the gram weight of the biological base component gram weight in the fabric is about 120 g/square meter, and the biological base component in the base fabric is 160 g/square meter, so that the biological base content of the biological base bamboo fiber synthetic leather is 62%.
Cutting the biological bamboo fiber synthetic leather prepared by the embodiment of the application into round samples with the diameter of 10mm, respectively transferring 0.5mL of staphylococcus aureus, escherichia coli, candida albicans and klebsiella pneumoniae into beef broth, culturing for 24 hours at 37 ℃, diluting the concentration of the culture solution to 10 < -5 > CFU/mL, preparing to-be-detected bacterial liquid, sucking 0.5mL of to-be-detected bacterial liquid drop onto the surface of the sample, continuously culturing for 6 hours at 37 ℃, using sterilized water subjected to sterilization operation to wash the sample, collecting the washing liquid, sucking 0.5mL of washing liquid, culturing for 12 hours on the culture medium, observing the colony count, calculating the antibacterial rate by utilizing the formula (the colony count of a blank group-the colony count of an experiment group)/the colony count of the blank group, and simultaneously performing a blank experiment, wherein the antibacterial rate of the biological bamboo fiber synthetic leather on staphylococcus aureus, escherichia coli, candida albicans and klebsiella pneumoniae on the experimental surface is more than 90%.
The biological-based bamboo fiber synthetic leather sample prepared by the embodiment of the application is detected according to a cup method of a GB 1037-1988 plastic film and sheet water vapor permeability test method, the detection results are shown in the following table, and the experimental data show that the biological-based bamboo fiber synthetic leather is environment-friendly, has the characteristics of moisture absorption, air permeability, antibiosis, bacteriostasis and the like, and can be widely applied to inner leather of bags and shoes.
In order to better understand the technical content of the present application, the following provides specific examples to further illustrate the present application. In the following examples, the impregnating resin was a bio-based high modulus impregnating resin, and it was free of fluorine-containing compounds, and its solid content was 40%, the percentage modulus was 17-21MPa, the breaking strength was > 45MPa, the elongation was not less than 200%, and the bio-based content was > 40%.
The surface layer resin is a fluorine-free bio-based hydrolysis resistant polyester polyether blend resin, the solid content is 32% -34%, the modulus is 7.0-9.0Mpa, the breaking strength is more than 30MPa, the viscosity range is 25-30 ten thousand CPS/25 ℃, and the bio-based content is more than 40% (both resins are purchased from Asahi chemical Co., ltd.).
Tear resistance aid XCW-08WH (available from Asahi chemical Co., ltd.), surfactant S-7 (available from Shanghai daily Polymer materials Co., ltd.), surfactant S-11 (available from Shanghai daily Polymer materials Co., ltd.), hydrolysis resistance aid SI-121 (available from Milti chemical Co., ltd.), leveling agent HS-1868 (available from Minglong chemical Co., ltd.), hygroscopic bacteriostasis aid DO-90 (available from Shanghai tile plus Biotech Co., ltd.).
Example (shown in FIG. 1)
(1) The bamboo fiber non-woven fabric with the thickness of 0.45mm is square, passes through a cloth storage frame, is subjected to needling reinforcement through a needling machine, and is then subjected to rolling shaping by a hot roller (the temperature of the hot roller is controlled to be 60-70 ℃) shaping, so that the double-layer composite bamboo fiber non-woven fabric with the thickness of 0.80mm can be prepared.
(2) The treated double-layer composite bamboo fiber non-woven fabric is firstly subjected to cloth storage frame, the speed of the cloth is 10m/min, and then is subjected to an impregnation tank with impregnation materials, and the pressure of an impregnation oil press roll is controlled to be 5-5.5Kg. After impregnation, the sugar degree is 30-32% through pre-solidification liquid, the pressure of a pre-solidification oil press roller is controlled to be 5-5.5Kg, the pre-solidification oil press roller is further subjected to a six-round ironing device (the ironing temperature is controlled to be 50 ℃), and finally the pre-solidification oil press roller is subjected to a coating table device provided with a coating knife, and meanwhile, fabrics prepared according to the method are coated on non-woven fabrics along a scraper. The gap between the coating layers is controlled to be 1.9-2.0mm, and the coating weight is controlled to be 1.1+/-0.05 kg/y.
The impregnation material is prepared by the following steps: bio-based impregnating resin: n, N dimethylformamide: leveling agent: tear resistance aids: nonionic surfactant: the moisture absorption and bacteriostasis auxiliary agent is prepared from the following components in percentage by weight: 180:1:15:1:1 weight ratio, stirring at room temperature at 1000r/min for 15-20 min to completely dissolve, and controlling viscosity at 200-260cps.
(3) The coated surface layer enters a three-fold solidification tank (the water solidification length reaches 84 meters, the solidification time is 8.4 minutes, and the solidification speed is 10 meters/minute) with the length of 30 meters, the solidification sugar degree is 18-21%, and the temperature is 30+/-2 ℃.
The configuration of the fabric comprises the following steps: biobased polyester polyether blend resin: n, N-dimethylformamide: hydrolysis resistance auxiliary agent: surfactant 1:surfactant 2:filler is added at a weight ratio of 100:50:0.5:1:1.5:20, the fabric is stirred at a stirring speed of 1500r/min at normal temperature for 30-35 min until the fabric is completely dissolved, the stirring speed is reduced to 300+/-50 r/min until the slurry is uniform, vacuum defoaming is carried out for 90min, and the viscosity is controlled to 12000cps-15000cps (temperature 35 ℃).
(4) After the semi-finished product of the synthetic leather comes out of the coagulation tank, the thickness is controlled to be 1.20-1.25mm, and the breadth is controlled to be 1.43-1.46m. Then the water enters a water washing tank (15 groups), the water washing sugar degree of the first six groups is controlled to be 10-20%, the water washing sugar degree of the middle six groups is controlled to be 0-10%, and the water washing sugar degree of the last three groups is controlled to be 0%; the temperature of the water washing tanks of the last three groups is controlled at 70-80 ℃.
(5) The bass after the water outlet washing tank is pre-scalded by eight rounds of scalding rollers (the temperature is 110+/-10 ℃); the pre-scalded bass is dried by a baking oven, and the temperature of the baking oven sequentially passes through is as follows: the first group of ovens has a temperature of 150 ℃, the second to fourth groups of ovens has a temperature of 160 ℃, and the fifth group of ovens has a temperature of 140 ℃ until complete drying. The thickness of the rolled paper after drying is 1.18-1.23mm, and the width is 143-146cm.
(6) The produced bio-based bamboo fiber synthetic leather is tested to be peeled off in pairs of three centimeters to reach 50N/3cm; softness values between 1.8 and 2.2 were tested by a softness tester. By observing the structure of the cell layer by using a magnifier, the distribution of cells is uniform, and the compact layer is thinner, thus having good moisture absorption and air permeability.
As can be seen from the above examples, the base cloth of the present application is a double-layer composite 100% bamboo fiber base cloth, the fabric and the impregnating material are both prepared from fluorine-free bio-based polyester polyether polyurethane resin with bio-based content higher than 40%, and the formula has better hand feeling by adjusting the size of the cells by adding cellulose. The application adjusts the machine process, combines the wet process flow with the bamboo fiber base cloth, and the bio-based content of the synthetic leather produced by the base cloth is up to 60 percent, the air permeability is good, the rebound resilience is good, and the bio-based bamboo fiber synthetic leather has the characteristics of environmental protection, moisture absorption, air permeability, antibiosis, bacteriostasis and the like, and can be widely applied to the inner leather of bags and suitcases.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the bio-based bamboo fiber synthetic leather is characterized by comprising the following steps of:
taking 100% bamboo fiber non-woven fabric as a substrate;
sequentially carrying out impregnation material rolling, pre-solidifying, coating fabric, solidifying to obtain a semi-finished product, wherein the impregnation material adopts fluorine-free bio-based high-modulus impregnation resin, the coating process adopts bio-based polyester polyether blending resin, and cellulose is added to adjust the hardness;
and washing the solidified semi-finished product with water, and heating and drying to obtain the bio-based bamboo fiber synthetic leather.
2. The method for preparing the bio-based bamboo fiber synthetic leather according to claim 1, wherein the method comprises the following steps: the non-woven fabric substrate is prepared by needling a double-layer composite 100% bamboo fiber spunlaced non-woven fabric and then performing hot roller rolling shaping.
3. The method for preparing the bio-based bamboo fiber synthetic leather according to claim 1 or 2, wherein the method comprises the following steps: the impregnating material is prepared by stirring and mixing fluorine-free bio-based high-modulus impregnating resin, an anti-tearing auxiliary agent, a moisture absorption antibacterial auxiliary agent, a leveling agent and a first solvent; the biobased content of the fluorine-free biobased high-modulus impregnating resin is more than 40%, and the room temperature viscosity of the impregnating material is controlled between 200 and 260cps.
4. A method for preparing the bio-based bamboo fiber synthetic leather as claimed in claim 3, wherein: the sizing agent of the coating fabric is fluorine-free and is obtained by stirring and mixing bio-based polyester polyether blend resin, cellulose, a surfactant and a second solvent; the mixed slurry is stirred for 30-35 minutes at the stirring speed of 1000-1500r/min at normal temperature.
5. The method for preparing the bio-based bamboo fiber synthetic leather according to claim 4, wherein the method comprises the following steps: in the process of coating the fabric by using the slurry, the weight ratio of the polyester polyether blend resin to the cellulose is 100:20, wherein the slurry has a room temperature viscosity of 12000-15000cps.
6. The method for preparing the bio-based bamboo fiber synthetic leather according to claim 4, wherein the method comprises the following steps: the first solvent and the second solvent are both N, N-dimethylformamide; the color paste is added into the impregnating material and/or the coating slurry.
7. The method for preparing the bio-based bamboo fiber synthetic leather according to claim 1, wherein the method comprises the following steps: the solidification in the solidification tank adopts a three-layer solidification mode, and the machine trolley speed is 9-10m/min.
8. The method for preparing the bio-based bamboo fiber synthetic leather according to claim 7, wherein the method comprises the following steps: the thickness of the solidified semi-finished product is controlled to be 1.25-1.30 mm; the washing device is provided with a plurality of groups of washing tanks, wherein the temperature of the final washing is controlled to be 70-80 ℃.
9. The method for preparing the bio-based bamboo fiber synthetic leather according to claim 1, wherein the method comprises the following steps: the heat drying includes: the hot roller is pre-heated at 100-120 ℃, and then dried at 145-165 ℃.
10. A biobased bamboo fiber synthetic leather prepared by the method for preparing the biobased bamboo fiber synthetic leather according to any one of claims 1-9, wherein the thickness is 1.18-1.23mm, and the softness test value is between.1.8-2.2.
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