CN103774457A - Preparation method of continuous-fiber microfiber leather - Google Patents
Preparation method of continuous-fiber microfiber leather Download PDFInfo
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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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Abstract
The invention relates to a preparation method of continuous-fiber microfiber leather. A leather base cloth adopts a continuous superfine fiber non-woven fabric which is subjected to sizing to form a water-soluble material layer on the surface of the fiber; the treated leather base cloth is impregnated with polyurethane (PU) with a wet-process coating technique, and carrying out coagulating bath treatment to remove the water-soluble material on the surface of the fiber, wherein a superfine fiber bundle-medullary sheath structure is formed between the fiber and the PU.
Description
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. a preparation method for the super fine leather of continuous fibers, it is continuous superfine fibre that feature is to remove from office fiber in base cloth, utilizes before wet-process coating technique impregnation polyurethane (PU), continuous fibers has been opened fibre.Before impregnation PU, utilize and pad or impregnation technology, leather base cloth is carried out to sizing finish; After oven dry, fiber or fibre bundle surface form one layer of polymeric coverlay; After wet-process coating, by destarch processing, the polymer on fiber or fibre bundle surface is eliminated, between fiber and PU, form " superfine fibre bundle-myelin " structure, the i.e. microstructure of similar corium.
2. preparation method according to claim 1, the super fine nonwoven fabric single fiber fineness of continuous fibers is at 0.01-6 μ m, and weight per unit area is at 40g/m
2-500g/m
2.
3. preparation method according to claim 1, sizing finish slurry used is water-soluble polymer, can be natural or synthetic, acid, alkali, oxidant or reductant have hydrolysis or degradation to it, or its hydrolysis of catalysis or degraded, comprise cellulose and derivative thereof, 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.
4. preparation method according to claim 1, the leather base cloth rate of sizing is at 0.2%-10%.When leather base cloth starching, adopt and flood, pad, repeatedly pad or the mode of blade coating is carried out.
5. preparation method according to claim 1, PU coating agent solvent for use comprises dimethyl formamide, toluene, dimethylbenzene, MEK, oxolane etc., can use separately or mix use.
6. preparation method according to claim 1, 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, 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.
7. preparation method according to claim 1, is applicable to PAUR and EU.
8. preparation method according to claim 1, while adopting alkaline destarch, adds the NaOH of 5-20g/L in water, be then washed to neutrality.For oxidation destarch, in water, add hydrogen peroxide 2-10g/L, NaOH 2-10g/L, processes after washing to neutral.Destarch temperature 40-95 ℃, time 15-60min.Wetting agent 0.2-2g/L in destarch solution.
9. the super fine leather of continuous fibers that according to claim 1 prepared by method can be used for manufacturing imitation leather garment material, lining.
10. the super fine leather of continuous fibers that according to claim 1 prepared by method can be used for manufacturing footwear leather, lining leather and liner leather.
The super fine leather of 11. continuous fibers that according to claim 1 prepared by method can be used for manufacturing luggage leather and lining.
The super fine leather of 12. continuous fibers that according to claim 1 prepared by method can be used for manufacturing furniture leather and lining.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105256602A (en) * | 2015-11-10 | 2016-01-20 | 陕西科技大学 | Manufacturing method for waterborne polyurethane superfine 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 |
| 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 |
| 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 simulated leather ramie fabric coating agent |
| CN111844827A (en) * | 2020-07-23 | 2020-10-30 | 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 |
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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 |
| 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 |
| CN105442340B (en) * | 2015-11-09 | 2018-10-19 | 上海华峰超纤材料股份有限公司 | High-speed train chair high fire-retardance superfine fiber chemical leather and preparation method thereof |
| CN105442336B (en) * | 2015-11-09 | 2019-05-31 | 上海华峰超纤材料股份有限公司 | High fire-retardance high-speed train chair superfine fiber chemical leather and preparation method thereof |
| 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 |
| CN105256602A (en) * | 2015-11-10 | 2016-01-20 | 陕西科技大学 | Manufacturing method for waterborne polyurethane superfine 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 |
| 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 |
| CN107987364B (en) * | 2017-12-29 | 2019-08-20 | 成都新柯力化工科技有限公司 | A kind of method that low cost prepares starch biological plastics |
| 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 simulated 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 simulated leather ramie fabric coating agent |
| CN111844827A (en) * | 2020-07-23 | 2020-10-30 | 天津工业大学 | Preparation method of microfiber leather facing 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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