CN103774457A - Preparation method of continuous-fiber microfiber leather - Google Patents

Preparation method of continuous-fiber microfiber leather Download PDF

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CN103774457A
CN103774457A CN201410037965.8A CN201410037965A CN103774457A CN 103774457 A CN103774457 A CN 103774457A CN 201410037965 A CN201410037965 A CN 201410037965A CN 103774457 A CN103774457 A CN 103774457A
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leather
fiber
preparation
water
lining
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钱晓明
宋卫民
肖鹏远
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LANGFANG CHINATEX NONWOVENS CO Ltd
Tiangong University
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LANGFANG CHINATEX NONWOVENS CO Ltd
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Abstract

本发明涉及一种连续纤维超纤革的制备方法。革基布采用连续超细纤维无纺布，通过“上浆”，使纤维表面包覆一层水溶性材料；然后利用湿法涂层工艺，将处理过的革基布含浸聚氨酯(PU)，经凝固浴处理后，除净纤维表面包覆的水溶性材料，纤维与聚氨酯(PU)之间形成“超细纤维束-髓鞘”结构。The invention relates to a preparation method of continuous fiber microfiber leather. The leather base fabric is made of continuous ultra-fine fiber non-woven fabric, and the surface of the fiber is covered with a layer of water-soluble material through "sizing"; then, the treated leather base fabric is impregnated with polyurethane (PU) by wet coating process. After the coagulation bath treatment, the water-soluble material coated on the surface of the fiber is removed, and a "ultrafine fiber bundle-myelin sheath" structure is formed between the fiber and polyurethane (PU).

Description

The preparation method of the super fine leather of a kind of continuous fibers
Technical field
The present invention relates to fabric and coating processing technique field thereof, its content is about the technology of preparing of the super fine leather of a kind of continuous fibers.The present invention is intended to solve the Construct question of " superfine fibre bundle-myelin " structure while utilizing the super fine leather of the super fine nonwoven fabric preparation of continuous fibers, make the super fine leather of continuous fibers obtain the microstructure of similar corium, outward appearance, feel, processing and serviceability meet or exceed corium.Meanwhile, the problem of wettability and poor permeability in the super fine nonwoven fabric wet method coating process of solution continuous fibers.Finally, expand the purposes of the super fine nonwoven fabric of continuous fibers, increase associated downstream product kind.
Background technology
The leather base cloth of manufacturing at present super fine leather is sea-island composite fiber short fiber nonwoven fabric, opens fine processing and make super fine leather after polyurethane (PU) wet-process coating.In the super fibre of fabric of island-in-sea type used, sea component is solubility polyester, and island component is polyamide.Utilize the difference of the two hydrolysis property under alkali condition or in different solvents deliquescent difference, through alkaline solution or solvent processing, polyester is removed, polyamide fiber bundle and PU form " superfine fibre bundle-myelin " structure.
This super fine leather technique is obviously inapplicable for non-sea-island composite fiber nonwoven fabric and the super fine nonwoven fabric of continuous fibers, continuously superfine fibre has been opened fibre and without dissolving component before finished leather, cannot obtain " superfine fibre bundle-myelin " structure, be difficult to obtain leather effect.In addition, the ultra-fine short fiber nonwoven fabric of fabric of island-in-sea type also has following problem as leather base cloth: be 1. difficult to Accurate Prediction and open the impact of fine rear super fine nonwoven fabric on synthetic leather physical and mechanical properties; 2. after sea component dissolves, component whole bundle in PU cavernous body myelin in polyamide island distributes, and does not superly carry out fibre fineness allotment when fine if manufactured, respectively restraint super fine will be uniform, in this and corium, the distribution of collagen fabric bundle is not inconsistent; 3. in order to reach the fibre of opening to a certain degree, the super fine leather of PU will stand stronger mechanism under alkali condition, and the performance of leather can be affected.Although these problems do not affect the commodity production of the super fine leather in island, the in-depth to product quality and raising can cause obstruction.
Summary of the invention
The present invention adopts the super fine nonwoven fabric of continuous fibers as leather base cloth, and before wet-process coating, base cloth has been opened fibre or base cloth itself and finely directly formed by super.The optional expanded range of leather base cloth, the impact that after coating, base cloth causes product physical and mechanical properties can be predicted comparatively exactly, improves quality and the emulation degree of product.Adopt the method for the invention can prepare the super fine leather of microcosmic " superfine fibre bundle-myelin " structure.
Technological process of the present invention and related description are as follows:
Technological process: continuous fibers super fine nonwoven fabric → " starching " → wet-process coating → " destarch " → product processing.
1, the super fine nonwoven fabric of continuous fibers is front in " starching ", has opened fibre, opens fine degree depending on final products style and performance requirement, opens fine rate at 20%-99%, and weight per unit area is at 40g/m 2-500g/m 2.After starching, fiber surface forms " pulp layer " of even thickness; After wet-process coating, in removing coagulating bath solvent or afterwards, will " pulp layer " from the interior Ex-all of super fine leather." slurry " is water soluble polymer, can be natural or synthetic, and acid, alkali, oxidant or reductant have hydrolysis or degradation to it, or its hydrolysis of catalysis or degraded, accelerates its removal from super fine leather, has following character when " starching ":
(1) slurries are good to super fine wettability, can use if desired surfactant, reduce slurry surface tension force, make that it is easy to sprawl at fiber surface, levelling;
(2) filming performance is good, to become epithelium not occur in typical wet-process coating agent swelling;
(3) easily remove.Can be fast from fiber surface dissociation, the slurry viscosity of backing off is low, easily from the gap of PU and fiber, washes out.
" slurry " is cellulose and derivative, starch and derivative thereof, converted starch, gelatin, alginate, polyvinyl alcohol, polyester polymer, polyacrylamide polymer and copolymer thereof, polyacrylate polymers and copolymer thereof, polyacrylonitrile base polymer and copolymer thereof.Can be used alone, also can mix use.For example, the polycondensation reaction of polyester easily occurs, and extent of polymerization is easily controlled, and monomer range of choice is wider, and polymer property is easily adjusted.By the adjustment to condensation monomer, can realize good adhesion to fiber and low viscosity again; Can also realize low surface tension and good permeability simultaneously.Common polyester pulp is easy to dissolve in boiling water; When mass percent is 6%, its viscosity is less than 6mPs; Can form good epithelium at fiber surface.Under alkali condition, can quick destarch in the water of 80 ℃.This base polymer is also very little to the pollution of environment, can realize biodegradation.
Control slurry the coated weight of fiber surface (after being starching before the gain in weight of nonwoven fabric and starching the ratio of nonwoven fabric weight) with " rate of sizing ", thereby control in sheath-like structure the size in space between fiber and PU." slurry " should have suitable viscosity, is beneficial on micro-scale film forming even.Balance between slurry stream levelling and viscosity can regulate by the molecular weight of " slurry " molecule, type of stock, solvent composition, surfactant, additive etc.According to weight per unit area and the porosity of leather base cloth, rate of sizing 0.2%-10%.When leather base cloth starching, adopt and flood, pad, repeatedly pad or the mode of blade coating is carried out.After starching, according to the character of different slurries, 50-150 ℃ of oven dry, can coordinate tentering simultaneously.
Superfine fibre specific area is large, and for the liquid that can infiltrate at fiber surface, the degree that it is sprawled and speed all can be accelerated greatly.Suitable surfactant can be strengthened this effect, and when particularly " slurries " viscosity is higher, because the equivalent capillary radius of superfine fibre net is very little, some space liquid will be difficult to enter, and the effect of surfactant is more important.For different slurries, need choose different surfactants, conventionally select anion or non-ionic surface active agent, or the two mixing use, consumption is the 0.05%-2% of sizing liquor weight.
2,, in the technique of PU wet-process coating, for the leather base cloth after " starching ", need to make corresponding adjustment:
First be the solvent of PU.The organic solvent using in the present invention comprises dimethyl formamide, toluene, dimethylbenzene, MEK, oxolane etc., can use separately or mix use.Apolegamy is when solvent, except consider coating agent viscosity, regulate setting rate, be adjusted to hole shape and density, adjusting evaporation rate etc., also to consider the effect to serous coat: in phase transition process, it is swelling that solvent can not make serous coat occur.For example, while adopting polyvinyl alcohol as slurry, PU solvent is selected dimethyl formamide and dimethylbenzene, and the two mass ratio is 95: 5.
Next is PU coagulating bath.In super fine leather wet-process coating technique, the processing of PU resin in coagulating bath is a very important link, in this stage, under the effect of concentration gradient formula, there is convection current in PU coating agent solvent and coagulating bath solvent, PU undergoes phase transition and separates out on coagulating bath interface, solidify gradually, form, the density etc. of hole is closely related with curing condition.Coagulating bath solvent is the mixed solvent of dimethyl formamide and water, and wherein dimethyl formamide volume fraction in mixed solvent is 10%-55%, and temperature is 20-65 ℃, and the processing time is 0.5-30min.In coagulating bath, surfactant is anion surfactant and non-ionic surface active agent, adjusts space form and the perforate degree of PU, and consumption is the 0.05%-2% of coagulating bath quality.In coagulating bath, contain inorganic salts: metal chloride, as sodium chloride, lithium chloride, calcium chloride, magnesium chloride; Metal sulfate, as sodium sulphate, magnesium sulfate; Metal carbonate and bicarbonate, as sodium carbonate, sodium bicarbonate; Metal phosphate, as sodium phosphate.
The method of the invention is applicable to PAUR and EU.About other additives, look product demand such as cellulose, lignin, calcium carbonate, wollastonite and various organic and inorganic pigment, fire retardant, antioxidant, anti ultraviolet agent, antiseptic and add.
Wet-process coating implementing process is: starching leather base cloth is through repeatedly padding, scrape slurry, immerses coagulating bath after reaching the band slurry amount of setting.
3, " destarch " stage, according to slurry therewith, determine desizing condition.For EU, can in water, add alkaline agent, promote the swelling and stripping of slurry.As polyacrylate, polyesters slurry, can in water, add the NaOH of 5-20g/L, carry out destarch processing, then wash with water to neutrality.For the slurry with oxidation or deoxidization, degradation, can in water, add oxidant or reductant, promote slurry hydrolysis, improve destarch efficiency.As polyvinyl alcohol pulp, can in water, add 30% hydrogen peroxide 2-10g/L, NaOH 2-10g/L, carries out destarch processing, is then washed to neutrality.
Destarch temperature 40-95 ℃, time 15-60min.In destarch solution, can add the wetting agent of 0.2-2g/L.
4, product processing.The super fine leather of continuous fibers obtaining, through further processing and arrangement, can be developed diversified product.If slim super fine leather is through two-sided napping arrangement and soft finish, can make artificial suede; Super fine leather one side intumescent coating after napping, then does the direct coating of PU, can be made into smooth leather, through cotton ginning, stamp processing, can make embossing leather, stamp leather, coordinates embossing finishing can make decorative pattern to have the super fine leather of stereoeffect after stamp.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1 suede
Leather base cloth is the super fine nonwoven fabric of continuous fibers, and weight per unit area is 100g/m 2, thickness is 0.8mm.Opening fine rate is 95%, and fiber average fineness is 4 μ m.
It is 2500 that material is selected polyvinyl alcohol, viscosity average molecular weigh.Sizing liquor solid content is that 5%, JFC mass percent is 1.5%, separately adds a small amount of defoamer and levelling agent.Leather base cloth two soak two roll after, liquid carrying rate is controlled at 75%-80%, on stenter 80 ℃ dry 2min.
In wet-process coating technique, select the special EU of super fine leather.When in this example, polyurethane solid content is 30%, 25 ℃, viscosity is 120Pas, and 100% modulus is 8.0MPa.Coating agent is take dimethyl formamide as solvent, and the content of PU in coating agent is 15%, and viscosity is 2700m Pas; The mass percent of anionic bleeding agent is 1.5%, and nonionic foam stabilizer mass percent is 2%; Separately add a small amount of defoamer.The impregnation in coating slurry of starching leather base cloth, roll compacting 4 times, pressure roller pressure is 0.7MPa.
Coagulating bath dimethyl formamide mass percent is 20%, and anion surfactant mass percent is 2%, and calcium chloride is 5g/L, and temperature is 40 ℃.In this example, the coagulating bath processing time is 5min.
Washing point two stages.First stage, NaOH 5g/L, 60 ℃ of water temperatures, pressure roller pressure is 0.1MPa; Second stage, 85 ℃ of water temperatures, clean 20min, and polyvinyl alcohol and dimethyl formamide are removed completely.120 ℃ of bake out temperatures.Surface of semi-finished is level and smooth, pore-free, and feel is flexible, and texture is plentiful, and skin sense is good.
Sanding finishing.Adopt conventional roughing-up machine to carry out sanding, emery cloth order number increases progressively, and is respectively 120,160,240 orders.Sanding roller rotating speed 600-1000r/min; The speed of a motor vehicle is controlled at 3-7m/min; 20 °-25 ° of wrap angles.Final grinding output controlling is at 10%-15%.
The suede making through above-mentioned technique has good " superfine fibre bundle-myelin " microstructure, and outward appearance is true to nature, and feel is abundant active, high resilience.Longitudinal stretching ultimate strength reaches 540N/5cm, and elongation at break reaches 62%; Cross directional stretch ultimate strength reaches 430N/5cm, and elongation at break reaches 67%.
Embodiment 2 embossing leather
The finished product making with embodiment 1 carries out embossing finishing.Process 135 ℃ of preheat temperatures, 160 ℃ of embossing roll temperatures, pressure 0.6MPa, speed of a motor vehicle 20m/min at special embossing machine.
The embossing leather decorative pattern making through above-mentioned technique is clear, effect stability.Longitudinal stretching ultimate strength reaches 524N/5cm, and elongation at break reaches 58%; Cross directional stretch ultimate strength reaches 415N/5cm, and elongation at break reaches 56%.
Embodiment 3 stamp leather
Stamp can be realized by transfering printing process or ROTARY SCREAM PRINTING technique.This example is transfer printing.
The semi-finished product that embodiment 1 obtains, dry coating is carried out on surface.PU mass percent 50% in coating agent, dimethyl formamide mass percent 45%, wood powder 4%, levelling agent 1%.25 ℃ of coating agent viscosity are about 6000cPas.Coating weight 100g/m 2, speed of a motor vehicle 6m/min.In coagulating bath, dimethyl formamide mass percent is 15%, and other conditions are identical with embodiment 1.
Washing is carried out transfer printing after drying.Calico paper is common PU leather transfer printing paper, on hot press, processes.It is 120 ℃ that heat is rolled temperature, pressure 2MPa, time 3-5s.
The stamp leather floral designs that make through above-mentioned technique are clear, and color is full, rediscover.Longitudinal stretching ultimate strength reaches 522N/5cm, and elongation at break reaches 54%; Cross directional stretch ultimate strength reaches 420N/5cm, and elongation at break reaches 52%.

Claims (12)

1.一种连续纤维超纤革的制备方法，特点在于革基布中纤维为连续超细纤维，利用湿法涂层工艺含浸聚氨酯(PU)以前，连续纤维已开纤。在含浸PU前，利用浸轧或浸渍工艺，对革基布进行上浆整理；烘干后，纤维或纤维束表面形成一层聚合物覆盖膜；湿法涂层后，通过退浆处理，将纤维或纤维束表面的聚合物除尽，纤维与PU之间形成“超细纤维束-髓鞘”结构，即类似真皮的微观结构。1. A preparation method of continuous fiber microfiber leather, characterized in that fiber in the leather base cloth is continuous superfine fiber, before utilizing the wet coating process to impregnate polyurethane (PU), the continuous fiber has been opened. Before impregnating PU, use padding or dipping process to sizing the leather base cloth; after drying, a layer of polymer covering film is formed on the surface of fibers or fiber bundles; after wet coating, desizing treatment, the fibers Or the polymer on the surface of the fiber bundle is removed, and a "ultrafine fiber bundle-myelin sheath" structure is formed between the fiber and PU, which is a microstructure similar to the dermis. 2.根据权利要求1所述制备方法，连续纤维超纤无纺布单纤细度在0.01-6μm，单位面积重量在40g／m2-500g／m2。2. The preparation method according to claim 1, wherein the single fiber fineness of the continuous fiber superfiber non-woven fabric is 0.01-6 μm, and the weight per unit area is 40 g/m 2 -500 g/m 2 . 3.根据权利要求1所述制备方法，上浆整理所用的浆料为水溶性聚合物，可以是天然的或合成的，酸、碱、氧化剂或还原剂对其具有水解或降解作用，或催化其水解或降解，包括纤维素及其衍生物、淀粉及其衍生物、变性淀粉、明胶、海藻酸盐、聚乙烯醇、聚酯类聚合物、聚丙烯酰胺类聚合物及其共聚物、聚丙烯酸酯类聚合物及其共聚物、聚丙烯腈类聚合物及其共聚物。可单独使用，也可混合使用。3. according to the described preparation method of claim 1, the used slurry of sizing finishing is water-soluble polymer, can be natural or synthetic, and acid, alkali, oxidizing agent or reductive agent have hydrolysis or degradation to it, or catalyze its Hydrolysis or degradation, including cellulose and its derivatives, starch and its derivatives, modified starch, gelatin, alginate, polyvinyl alcohol, polyester polymers, polyacrylamide polymers and their copolymers, polyacrylic acid Ester polymers and their copolymers, polyacrylonitrile polymers and their copolymers. Can be used alone or in combination. 4.根据权利要求1所述制备方法，革基布上浆率在0.2％-10％。革基布上浆时采用浸渍、浸轧、多次浸轧或刮涂的方式进行。4. The preparation method according to claim 1, the sizing rate of the leather base cloth is 0.2%-10%. The sizing of the leather base cloth is carried out by dipping, padding, multiple padding or scraping. 5.根据权利要求1所述制备方法，PU涂层剂所用溶剂包括二甲基甲酰胺、甲苯、二甲苯、甲乙酮、四氢呋喃等，可以单独使用或混合使用。5. according to the described preparation method of claim 1, the used solvent of PU coating agent comprises dimethylformamide, toluene, xylene, methyl ethyl ketone, tetrahydrofuran etc., can use alone or mixed use. 6.根据权利要求1所述制备方法，凝固浴溶剂为二甲基甲酰胺和水的混合溶剂，其中二甲基甲酰胺在混合溶剂中体积分数为10％-55％，温度为20-65℃，处理时间为0.5-30min。凝固浴中表面活性剂为阴离子表面活性剂和非离子表面活性剂，用量为凝固浴质量的0.05％-2％。凝固浴中含有无机盐：金属氯化物，如氯化钠、氯化锂、氯化钙、氯化镁；金属硫酸盐，如硫酸钠、硫酸镁；金属碳酸盐及碳酸氢盐，如碳酸钠、碳酸氢钠；金属磷酸盐，如磷酸钠。6. The preparation method according to claim 1, the coagulation bath solvent is a mixed solvent of dimethylformamide and water, wherein the volume fraction of dimethylformamide in the mixed solvent is 10%-55%, and the temperature is 20-65 ℃, the treatment time is 0.5-30min. The surfactants in the coagulation bath are anionic surfactants and nonionic surfactants, and the dosage is 0.05%-2% of the mass of the coagulation bath. The coagulation bath contains inorganic salts: metal chlorides, such as sodium chloride, lithium chloride, calcium chloride, magnesium chloride; metal sulfates, such as sodium sulfate, magnesium sulfate; metal carbonates and bicarbonates, such as sodium carbonate, Sodium bicarbonate; metal phosphates such as sodium phosphate. 7.根据权利要求1所述制备方法，适用于聚酯型聚氨酯和聚醚型聚氨酯。7. according to the described preparation method of claim 1, be applicable to polyester type polyurethane and polyether type polyurethane. 8.根据权利要求1所述制备方法，采用碱性退浆时，水中加入5-20g／L的氢氧化钠，然后水洗至中性。对于氧化退浆，水中加入双氧水2-10g／L，氢氧化钠2-10g／L，处理后水洗至中性。退浆温度40-95℃，时间15-60min。退浆溶液中润湿剂0.2-2g／L。8. The preparation method according to claim 1, when alkaline desizing is used, 5-20 g/L of sodium hydroxide is added to the water, and then washed to neutrality. For oxidative desizing, add 2-10g/L hydrogen peroxide and 2-10g/L sodium hydroxide to the water, wash with water until neutral after treatment. Desizing temperature 40-95 ℃, time 15-60min. The wetting agent in the desizing solution is 0.2-2g/L. 9.根据权利要求1所述方法制备的连续纤维超纤革可用于制造仿皮服装面料、衬里。9. the continuous fiber microfiber leather prepared by the method according to claim 1 can be used to manufacture imitation leather garment lining, lining. 10.根据权利要求1所述方法制备的连续纤维超纤革可用于制造鞋革、衬里革和内衬革。10. The continuous fiber microfiber leather prepared by the method according to claim 1 can be used to manufacture shoe leather, lining leather and inner lining leather. 11.根据权利要求1所述方法制备的连续纤维超纤革可用于制造箱包革及衬里。11. the continuous fiber microfiber leather prepared by the method according to claim 1 can be used to manufacture bag leather and lining. 12.根据权利要求1所述方法制备的连续纤维超纤革可用于制造家具革及衬里。12. The continuous fiber microfiber leather prepared by the method according to claim 1 can be used to manufacture furniture leather and lining.
CN201410037965.8A 2014-01-24 2014-01-24 Preparation method of continuous-fiber microfiber leather Pending CN103774457A (en)

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CN105256602A (en) * 2015-11-10 2016-01-20 陕西科技大学 Manufacturing method for waterborne polyurethane superfine fiber synthetic leather
CN105442336A (en) * 2015-11-09 2016-03-30 上海华峰超纤材料股份有限公司 High-inflaming-retarding ultrafine fiber synthetic leather for high-speed train seat and preparation method of high-inflaming-retarding ultrafine fiber synthetic leather
CN105442340A (en) * 2015-11-09 2016-03-30 上海华峰超纤材料股份有限公司 High-inflaming-retarding ultrafine fiber synthetic leather for high-speed train seat and preparation method of high-inflaming-retarding ultrafine fiber synthetic leather
CN105463865A (en) * 2015-12-22 2016-04-06 上海华峰超纤材料股份有限公司 Cowhide-imitated microfibre synthetic leather and manufacturing method thereof
CN106436342A (en) * 2016-11-15 2017-02-22 福建华夏合成革有限公司 Ultra-soft protein synthetic leather and preparing method thereof
CN107987364A (en) * 2017-12-29 2018-05-04 成都新柯力化工科技有限公司 A kind of method that low cost prepares starch biological plastics
CN109610189A (en) * 2018-11-20 2019-04-12 武汉纺织大学 A kind of preparation method of imitation leather ramie fabric coating agent
CN111844827A (en) * 2020-07-23 2020-10-30 天津工业大学 A kind of preparation method of superfiber veneer leather surface layer film with microporous channel
CN113417151A (en) * 2021-07-08 2021-09-21 江苏聚杰微纤科技集团股份有限公司 Environment-friendly PU artificial leather with oily-like cellular structure and preparation method thereof

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CN105442340A (en) * 2015-11-09 2016-03-30 上海华峰超纤材料股份有限公司 High-inflaming-retarding ultrafine fiber synthetic leather for high-speed train seat and preparation method of high-inflaming-retarding ultrafine fiber synthetic leather
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CN105256602B (en) * 2015-11-10 2017-06-20 陕西科技大学 A kind of manufacture method of aqueous polyurethane superfine fiber synthetic leather
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CN105463865A (en) * 2015-12-22 2016-04-06 上海华峰超纤材料股份有限公司 Cowhide-imitated microfibre synthetic leather and manufacturing method thereof
CN106436342A (en) * 2016-11-15 2017-02-22 福建华夏合成革有限公司 Ultra-soft protein synthetic leather and preparing method thereof
CN106436342B (en) * 2016-11-15 2019-05-21 福建华夏合成革有限公司 A kind of ultra-soft protein synthetic leather and preparation method thereof
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CN107987364A (en) * 2017-12-29 2018-05-04 成都新柯力化工科技有限公司 A kind of method that low cost prepares starch biological plastics
CN109610189A (en) * 2018-11-20 2019-04-12 武汉纺织大学 A kind of preparation method of imitation leather ramie fabric coating agent
CN109610189B (en) * 2018-11-20 2019-11-08 武汉纺织大学 A kind of preparation method of leather-like ramie fabric coating agent
CN111844827A (en) * 2020-07-23 2020-10-30 天津工业大学 A kind of preparation method of superfiber veneer leather surface layer film with microporous channel
CN111844827B (en) * 2020-07-23 2022-05-27 天津工业大学 Preparation method of microfiber leather facing layer film with microporous channel
CN113417151A (en) * 2021-07-08 2021-09-21 江苏聚杰微纤科技集团股份有限公司 Environment-friendly PU artificial leather with oily-like cellular structure and preparation method thereof
CN113417151B (en) * 2021-07-08 2023-01-03 江苏聚杰微纤科技集团股份有限公司 Environment-friendly PU artificial leather with oily-like cellular structure and preparation method thereof

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