CN102561052B - Method for producing superfine fiber synthetic leather - Google Patents
Method for producing superfine fiber synthetic leather Download PDFInfo
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- CN102561052B CN102561052B CN2012100106030A CN201210010603A CN102561052B CN 102561052 B CN102561052 B CN 102561052B CN 2012100106030 A CN2012100106030 A CN 2012100106030A CN 201210010603 A CN201210010603 A CN 201210010603A CN 102561052 B CN102561052 B CN 102561052B
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Abstract
The invention discloses a method for producing superfine fiber synthetic leather. The method includes subjecting a base fabric which is made of unfigured bi-component islands-in-sea fibers to heat setting, subjecting the base fabric to impregnation through an impregnation polyurethane sizing, coating at least one layer of a coating polyurethane sizing on the surface of the impregnated base fabric, obtaining a semi-finished product of the synthetic leather after solidification and rinsing, subjecting the semi-finished product of the synthetic leather to extraction and quantity reduction with the use of a solvent which can dissolve sea components in the islands-in-sea fibers, and obtaining the superfine fiber synthetic leather product through after finish of the reduced semi-finished product of the synthetic leather. Compared with the prior art, by means of the method for producing the superfine fiber synthetic leather, the problem of repetitive production of multiple processes of the solidification, the rinsing, drying, post-treatment of the base fabric and the like is avoided, the production process is shortened, production efficiency is improved, energy consumption is reduced, production cost is lowered, peeling strength of the manufactured product is high, the superfine fiber synthetic leather feels soft, elasticity is good, and the superfine fiber synthetic leather is closer to real leather.
Description
Technical field
The present invention relates to the synthetic leather preparing technical field, relate in particular to a kind of production method of superfine fiber chemical leather.
Background technology
superfine fiber chemical leather is the superfine twice-laid novel high-grade dermatine of a kind of use, it is three-dimensional network-like structure non-weaving cloth and a series of polyurethane ultrafine fiber synthetic leathers that process of high resilience polyurethane resin process made from the fabric of island-in-sea type bicomponent fiber, it is the of new generation high simulated composite leather that developed recently gets up, be called the 4th generation artificial leather, can compare favourably with senior natural leather, has the peculiar breathable moisture permeability of natural leather, and in chemical resistance, the mildew-resistant sex change, the aspects such as flexibility (adaptability) of operation have all surpassed natural leather, can be used as footwear, case and bag, furniture, the every field such as automotive trim, have the characteristic of corium and the physical index more superior than corium.
At present, the production of synthetic leather and research and development are always take natural leather as target, and the microstructure of superfine fiber chemical leather and outward appearance are all very near natural leather.The conventional production procedure of common coating superfine fiber chemical leather is: arrangement → synthetic leather finishing (embossing, printing etc.) after spinning (fabric of island-in-sea type bicomponent fiber) → nonwoven fabric → HEAT SETTING → impregnation polyurethane slurry → solidify, wash → solvent extraction → drying → base cloth processing (WATER REPELLENT TREATMENT) → coating polyurethane slurry → solidify, wash → base cloth.It is to make the three-dimensional network-like structure non-weaving cloth as base cloth take the fabric of island-in-sea type bicomponent fiber, first the synthetic leather base cloth of impregnation polyurethane slurry carried out the solvent extraction processing, sea component in the fabric of island-in-sea type bicomponent fiber of composition nonwoven fabric is removed, superfine fibre bundle and the microcellular structure of the polyurethane parcel after formation is solidified, thus produce superfine fiber synthetic leather base cloth; Carry out applying again polyurethane slurry after water-proof finish, form the coating layer on surface.Because the surface at base cloth has applied one deck (or multilayer) high molecular polymerization film, thereby give the Surface-micromachining process of its one or more function, met the demand of people to the product of different-style, difference in functionality.
In conventional production procedure, a base cloth treatment step is arranged after the impregnation polyurethane slurry, due to the method that usually adopts surface waterproofing to process, stop too fast causing of water migration rate to form moisture film on the surface of base cloth, the coating polyurethane slurry that is unfavorable for next step, even because hydraulic pressure is too high, form some balloon-shaped structures between at the bottom of base cloth surface and coat, reduce the peel strength of coated side and base cloth; And the secondary impregnation, solidify, produced and applied clearly interface between impregnation layer and coat, cause the product feel of producing partially firmly, even to have the paper sense, and have the defects such as peel strength is low.Generally speaking, the problems such as the expense that there is complex process in existing production technology, it is wayward to produce, poor product quality, base cloth are processed is higher, and multiple operation has carried out duplication of production (drying, solidify, the operation such as washing all carried out twice), not only lose time, the energy, and increased production cost.
Summary of the invention
Technical problem to be solved by this invention is:, for the deficiency that prior art exists, provide the production method of the superfine fiber chemical leather that a kind of production procedure is short, production cost is low, the product softness is good, peel strength is high.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of production method of superfine fiber chemical leather, the base cloth that figured type bi-component islands-in-sea type fibre not is made into, after HEAT SETTING, at first through the impregnation polyurethane slurry, base cloth is carried out impregnation, base cloth surface after impregnation applies one deck at least and applies polyurethane slurry again, then make the synthetic leather semi-finished product after solidifying and washing, use the solvent that can dissolve the sea component in described islands-in-sea type fibre to extract decrement described synthetic leather semi-finished product, then with the synthetic leather semi-finished product after decrement through after arrangement obtain the superfine fiber chemical leather product.
As a kind of preferred, described not figured type bi-component islands-in-sea type fibre is not figured type bi-component islands-in-sea type fibre of PA6/PE or PET/PE.
Described PA6/PE or PET/PE be figured type bi-component islands-in-sea type fibre not, with the polyester slice after nylon 6 or crystallizing and drying and the low density polyethylene (LDPE) mass ratio according to 50～60:50～40, by the screw extruder melting, controlling the spinning temperature scope is 245～285 ℃, through cooling quench (16～25 ℃ of wind-warm syndrome), drawing-off (4～6 times of drafting multiples), the operations such as (oil concentration are 4～10%) that oils, the 5～7D that spins out, nylon 6 or polyester be that island component, low density polyethylene (LDPE) are the not figured type bi-component islands-in-sea type fibre of sea component.
To be heated under 110～135 ℃ and by roll, be carried out HEAT SETTING by the nonwoven fabric that described not figured type bi-component islands-in-sea type fibre is made into, the density of the base cloth after HEAT SETTING is 0.20～0.35 g/cm
3, thickness is 1.4～3.0 mm.
Wherein, the preparation of described impregnation polyurethane slurry is adopted single or blending polyurethane resin method is modulated, by weight, in the DMF of 20～100 parts, add 1～4 part of bleeding agent, 1～4 part of curing agent, 1～4 part of defoamer and 1～20 part of mill base, stir 10～30min, then add 100 parts of polyurethane resins, then obtain the impregnation polyurethane slurry that solid content is 8～25wt% after stirring 60～100min.
Described bleeding agent is sulphosuccinates; Described defoamer is polypropylene glycerol aether; Described curing agent is Span.As a kind of preferred, described bleeding agent is anionic type, main component is Aerosol OT or sulfosuccinic acid double tridecyl ester sodium, and its effect is to strengthen infiltration and the wettability of polyurethane slurry to base cloth, can also improve the exchange velocity of water and DMF; The main component of described defoamer is polypropylene glycerol aether, and its effect is to eliminate in nonwoven fabric to bring polyurethane into and contain air in immersion liquid and slurry produce in whipping process bubble, increases the wettability between polyurethane and fiber; Described curing agent is nonionic, and main component is Span, and it is a kind of senior lipophilic emulsifier, and the fiber of nonwoven fabric is had good smoothing effect, can increase slip and the flexibility of synthetic leather; Described mill base mainly is comprised of resin carrier, pigment or dyestuff, DMF and auxiliary agent four parts, gives slurry different colors, produces the color series product; Described polyurethane resin is modulus 20～160Kg/cm
2, elastic extension is 400～500% and good polyester or the EU resin of solvent resistance.
As a kind of improvement, described coating polyurethane slurry is by weight, in the DMF of 30～60 parts, add 1～4 part of levelling agent, 1～4 part of bleeding agent, 1～4 part of curing agent, 1～4 part of defoamer and 1～20 part of mill base, stir 10～30min, then add 100 parts of polyurethane resins, then obtain the coating polyurethane slurry that viscosity is 8000～15000cps after stirring 60～100min and vacuum defoamation.
During described coating, base cloth after impregnation will be coated with and scrape slurry and be coated with and scrape on surface by coating head, and coating thickness is 0.6～1.6mm, and the speed of a motor vehicle is 2～10m/min, be coated with when the impregnation polyurethane slurry of by floating cutter, base cloth being taken out of before scraping scrapes off and be coated with and scrape, can not have air to enter in coating procedure.
Described levelling agent is for being the dimethyl silicone polymer of modification; Described bleeding agent is sulphosuccinates; Described defoamer is polypropylene glycerol aether; Described curing agent is Span.The effect of described levelling agent is that appropriateness reduces polyurethane slurry viscosity, improves its mobility, increases the compatibility of resin and base cloth; As a kind of preferred, described bleeding agent is anionic type, main component is Aerosol OT or sulfosuccinic acid double tridecyl ester sodium, and its effect is to strengthen infiltration and the wettability of polyurethane slurry to base cloth, can also improve the exchange velocity of water and DMF; The main component that described defoamer is is polypropylene glycerol aether, and its effect is to eliminate in nonwoven fabric to bring polyurethane into and contain air in immersion liquid and slurry produce in whipping process bubble, increases the wettability between polyurethane and fiber; Described curing agent is nonionic, and main component is Span, and it is a kind of senior lipophilic emulsifier, and the fiber of nonwoven fabric is had good smoothing effect, can increase slip and the flexibility of synthetic leather; Described mill base mainly is comprised of resin carrier, pigment or dyestuff, DMF and auxiliary agent four parts, gives slurry different colors, produces the color series product; Described polyurethane resin is modulus 20～160Kg/cm
2, elastic extension is 800～1000%, and solvent resistance is good, filming performance is good, swelling resistance, machinery powerful high polyester or EU resin in solvent.
Carry out in concentration 15～40wt%, temperature are the DMF aqueous solution of 25～35 ℃ during described solidifying, carry out in the cleaning sink that a plurality of temperature are set from low to high successively during described washing, the temperature of described a plurality of cleaning sinks is 25～70 ℃.
As a kind of preferred, use the pure toluene solution of 85～90 ℃ during described extraction decrement, during described extraction, the half-finished percentage elongation of synthetic leather is 2～5%.
Clean except desolventizing with boiling water after extraction, after oven dry, through drying, change and softly rub the post processing such as skin, and finishing etc. obtains product.
, owing to having adopted technique scheme, the invention has the beneficial effects as follows:
1, the present invention is after to base cloth impregnation polyurethane slurry, directly through being coated with cutter and paint roller, under the drive of paint roller, apply polyurethane slurry and be coated onto equably the base cloth surface by being coated with cutter, apply polyurethane slurry, and then the base cloth after applying is solidified, washing, remove DMF unnecessary in base cloth, upper strata forms the microcellular structure of different structure on thickness direction, lower floor forms larger polyurethane finger-type pore structure, then through the extraction decrement treatment, and base cloth post processing, compared to existing technology, avoided solidifying, washing, drying, the problem of the multiple operation duplications of production such as base cloth post processing, shortened production procedure, improved production efficiency, reduced energy resource consumption, reduced production cost, and the product impregnation layer of producing is combined with coat closely, not there will be obvious coating interface, the problem such as layering even, the product peel strength is high, peel strength＞80N/3cm, the product feel is more soft, good springiness, third dimension is strong, more close to corium.
2, the approaching coating polyurethane slurry raw material of the shrinkage factor of employing of the present invention and base cloth, and adopt suitable tension force when the extraction decrement, adjust synthetic leather semi-finished product suitable percentage elongation in extraction process, overcome in prior art apply after very easily curling in solvent extraction process, the delamination of product and be difficult for decrement, even the problem such as can't normally produce.
The specific embodiment
, below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1
With nylon 6 and the low density polyethylene (LDPE) mass ratio according to 50:50, by the screw extruder melting, controlling the spinning temperature scope is 245 ℃, through wet goods operation on the cooling quenches of 16 ℃, the drawing-off of 4 times, finish that concentration is 4wt%, spin out 5D, take nylon 6 as island component, low density polyethylene (LDPE) is the not figured type bi-component islands-in-sea type fibre of sea component.
It is that 1.60m, thickness are the base cloth of 1.50mm that figured type bi-component islands-in-sea type fibre not is made into fabric width, heats under 110 ℃ and by roll, carries out HEAT SETTING, and the density of the base cloth after HEAT SETTING is 0.20g/cm
3, thickness is 1.4mm.
Adopt single or blending polyurethane resin method is modulated the impregnation polyurethane slurry, by weight, in the DMF of 20 parts, 1 part of Aerosol OT, 1 part of polypropylene glycerol aether, 1 part of Span and 5 parts of mill bases, stir 10min, then add 100 parts of modulus 30Kg/cm
2, elastic extension is 400% polyester urethane resin, then obtains the impregnation polyurethane slurry that solid content is 8wt% after stirring 60min, and the base cloth after HEAT SETTING is carried out impregnation through impregnating groove to base cloth, Negotiation speed is 2m/min.
In the DMF of 30 parts, add the dimethyl silicone polymer of 1 part of modification, 1 part of Aerosol OT, 1 part of polypropylene glycerol aether, 1 part of Span and 1 part of mill base, stir 10min, then add 100 parts of modulus 30Kg/cm
2, elastic extension is 800% polyester urethane resin, obtain the coating polyurethane slurry that viscosity is 8000cps after stirring again 60min and vacuum defoamation, base cloth after impregnation will be coated with and scrape slurry and be coated with and scrape on surface by coating head, coating thickness is 0.6mm, the speed of a motor vehicle is 2m/min, be coated with when the impregnation polyurethane slurry of by floating cutter, base cloth being taken out of before scraping scrapes off and be coated with and scrape, can not have air to enter in coating procedure.
Base cloth after applying in being the DMF aqueous solution of 25 ℃, concentration 15wt%, temperature is solidified, then wash in the cleaning sink that 20 temperature are set from low to high successively, the temperature of described 20 cleaning sinks is 25～70 ℃, the temperature difference of each cleaning sink is 2～10 ℃, makes the synthetic leather semi-finished product after solidifying and washing.
Use the pure toluene solution of 85 ℃ to extract decrement the synthetic leather semi-finished product, during extraction, the half-finished percentage elongation of synthetic leather is 2%, sea component in islands-in-sea type fibre is extracted, after cleaning with boiling water, then with the synthetic leather semi-finished product after decrement through drying, change soft the arrangement after rubbing skin and finishing etc. and obtain the superfine fiber chemical leather product.
Embodiment 2
With nylon 6 and the low density polyethylene (LDPE) mass ratio according to 60:40, by the screw extruder melting, controlling the spinning temperature scope is 285 ℃, through wet goods operation on the cooling quenches of 25 ℃, the drawing-off of 6 times, finish that concentration is 10wt%, spin out 7D, the not figured type bi-component islands-in-sea type fibre take nylon 6 island components, low density polyethylene (LDPE) as sea component.
It is that 1.60m, thickness are the base cloth of 1.70mm that figured type bi-component islands-in-sea type fibre not is made into fabric width, heats under 135 ℃ and by roll, carries out HEAT SETTING, and the density of the base cloth after HEAT SETTING is 0.35 g/cm
3, thickness is 3.0 mm.
Adopt single or blending polyurethane resin method is modulated the impregnation polyurethane slurry, by weight, in the DMF of 100 parts, add 4 parts of sulfosuccinic acid double tridecyl ester sodium, 4 parts of polypropylene glycerol aethers, 4 parts of Spans and 20 parts of mill bases, stir 30min, then add 100 parts of modulus 160Kg/cm
2, elastic extension is 500% polyester urethane resin, then obtains the impregnation polyurethane slurry that solid content is 25wt% after stirring 100min, and the base cloth after HEAT SETTING is carried out impregnation through impregnating groove to base cloth, Negotiation speed is 10m/min.
In the DMF of 60 parts, add the dimethyl silicone polymer of 4 parts of modifications, 4 parts of sulfosuccinic acid double tridecyl ester sodium, 4 parts of polypropylene glycerol aethers, 4 parts of Spans and 20 parts of mill bases, stir 30min, then add 100 parts of modulus 160Kg/cm
2, elastic extension is 1000% polyester urethane resin, obtain the coating polyurethane slurry that viscosity is 15000cps after stirring again 100min and vacuum defoamation, base cloth after impregnation will be coated with and scrape slurry and be coated with and scrape on surface by coating head, coating thickness is 1.6mm, the speed of a motor vehicle is 10m/min, be coated with when the impregnation polyurethane slurry of by floating cutter, base cloth being taken out of before scraping scrapes off and be coated with and scrape, can not have air to enter in coating procedure.
Base cloth after applying in being the DMF aqueous solution of 35 ℃, concentration 40wt%, temperature is solidified, then wash in the cleaning sink that 18 temperature are set from low to high successively, the temperature of described 18 cleaning sinks is 25～70 ℃, the temperature difference of each cleaning sink is 2～10 ℃, makes the synthetic leather semi-finished product after solidifying and washing.
Use the pure toluene solution of 90 ℃ to extract decrement the synthetic leather semi-finished product, during extraction, the half-finished percentage elongation of synthetic leather is 5%, sea component in islands-in-sea type fibre is extracted, after cleaning with boiling water, then with the synthetic leather semi-finished product after decrement through drying, change soft the arrangement after rubbing skin and finishing etc. and obtain the superfine fiber chemical leather product.
Embodiment 3
With the polyester slice after crystallizing and drying and the low density polyethylene (LDPE) mass ratio according to 50:50, by the screw extruder melting, controlling the spinning temperature scope is 265 ℃, through wet goods operation on the cooling quenches of 20 ℃, the drawing-off of 5 times, finish that concentration is 8wt%, spin out 6D, take polyester as island component, low density polyethylene (LDPE) is the not figured type bi-component islands-in-sea type fibre of sea component.
It is that 1.60m, thickness are the base cloth of 1.60mm that figured type bi-component islands-in-sea type fibre not is made into fabric width, heats under 120 ℃ and by roll, carries out HEAT SETTING, and the density of the base cloth after HEAT SETTING is 0.25 g/cm
3, thickness is 2.0 mm.
Adopt single or blending polyurethane resin method is modulated the impregnation polyurethane slurry, by weight, in the DMF of 60 parts, add 3 parts of Aerosol OTs, 2 parts of polypropylene glycerol aethers, 2 parts of Spans and 10 parts of mill bases, stir 20min, then add 100 parts of modulus 90Kg/cm
2, elastic extension is 450% EU resin, then obtains the impregnation polyurethane slurry that solid content is 20wt% after stirring 80min, and the base cloth after HEAT SETTING is carried out impregnation through impregnating groove to base cloth, Negotiation speed is 8m/min.
In the DMF of 40 parts, add the dimethyl silicone polymer of 3 parts of modifications, 3 parts of Aerosol OTs, 2 parts of polypropylene glycerol aethers, 2 parts of Spans and 10 parts of mill bases, stir 30min, then add 100 parts of modulus 90Kg/cm
2, elastic extension is 900% EU resin, obtain the coating polyurethane slurry that viscosity is 12000cps after stirring again 80min and vacuum defoamation, base cloth after impregnation will be coated with and scrape slurry and be coated with and scrape on surface by coating head, coating thickness is 1.2mm, the speed of a motor vehicle is 8m/min, be coated with when the impregnation polyurethane slurry of by floating cutter, base cloth being taken out of before scraping scrapes off and be coated with and scrape, can not have air to enter in coating procedure.
Base cloth after applying in being the DMF aqueous solution of 30 ℃, concentration 30wt%, temperature is solidified, then wash in the cleaning sink that 10 temperature are set from low to high successively, the temperature of described 10 cleaning sinks is 25～70 ℃, the temperature difference of each cleaning sink is 2～10 ℃, makes the synthetic leather semi-finished product after solidifying and washing.
Use the pure toluene solution of 88 ℃ to extract decrement the synthetic leather semi-finished product, during extraction, the half-finished percentage elongation of synthetic leather is 3%, sea component in islands-in-sea type fibre is extracted, after cleaning with boiling water, then with the synthetic leather semi-finished product after decrement through drying, change soft the arrangement after rubbing skin and finishing etc. and obtain the superfine fiber chemical leather product.
Claims (8)
1. the production method of a superfine fiber chemical leather, it is characterized in that: will be not the base cloth that is made into of figured type bi-component islands-in-sea type fibre, after HEAT SETTING, at first through the impregnation polyurethane slurry, base cloth is carried out impregnation, base cloth surface after impregnation applies one deck at least and applies polyurethane slurry again, then make the synthetic leather semi-finished product after solidifying and washing, use the solvent that can dissolve the sea component in described islands-in-sea type fibre to extract decrement described synthetic leather semi-finished product, then with the synthetic leather semi-finished product after decrement through after arrangement obtain the superfine fiber chemical leather product; The preparation of described impregnation polyurethane slurry is by weight, in the DMF of 20～100 parts, add 1～4 part of bleeding agent, 1～4 part of curing agent, 1～4 part of defoamer and 1～20 part of mill base, stir 10～30min, then add 100 parts of polyurethane resins, then obtain the impregnation polyurethane slurry that solid content is 8～25wt% after stirring 60～100min; Described bleeding agent is sulphosuccinates; Described defoamer is polypropylene glycerol aether; Described curing agent is Span; Described polyurethane resin is modulus 20～160Kg/cm
2, elastic extension is 400～500% polyester or EU resin.
2. the production method of superfine fiber chemical leather as claimed in claim 1 is characterized in that: described not figured type bi-component islands-in-sea type fibre is not figured type bi-component islands-in-sea type fibre of PA6/PE or PET/PE.
3. the production method of superfine fiber chemical leather as claimed in claim 2, it is characterized in that: described PA6/PE or PET/PE be figured type bi-component islands-in-sea type fibre not, with nylon 6 or polyester slice and the low density polyethylene (LDPE) mass ratio according to 50～60:50～40, the 5～7D that spins out, nylon 6 or polyester be that island component, low density polyethylene (LDPE) are the not figured type bi-component islands-in-sea type fibre of sea component.
4. the production method of superfine fiber chemical leather as claimed in claim 1, it is characterized in that: the density of described base cloth after HEAT SETTING is 0.20～0.35g/cm
3, thickness is 1.4～3.0mm.
5. the production method of superfine fiber chemical leather as claimed in claim 1, it is characterized in that: described coating polyurethane slurry is by weight, in the DMF of 30～60 parts, add 1～4 part of levelling agent, 1～4 part of bleeding agent, 1～4 part of curing agent, 1～4 part of defoamer and 1～20 part of mill base, stir 10～30min, then add 100 parts of polyurethane resins, then stir after 60～100min and vacuum defoamation obtains the coating polyurethane slurry that viscosity is 8000～15000cps.
6. the production method of superfine fiber chemical leather as claimed in claim 5, it is characterized in that: described levelling agent is the dimethyl silicone polymer of modification; Described bleeding agent is sulphosuccinates; Described defoamer is polypropylene glycerol aether; Described curing agent is Span; Polyurethane resin in described coating polyurethane slurry is modulus 20～160Kg/cm
2, elastic extension is 800～1000% polyester or EU resin.
7. the production method of superfine fiber chemical leather as claimed in claim 1, it is characterized in that: carry out in concentration 15～40wt%, temperature are the DMF aqueous solution of 25～35 ℃ during described solidifying, carry out in the cleaning sink that a plurality of temperature are set from low to high successively during described washing, the temperature of described a plurality of cleaning sinks is 25～70 ℃.
8., as the production method of described any superfine fiber chemical leather of claim 2 to 7, it is characterized in that: use the pure toluene solution of 85～90 ℃ during described extraction decrement, during described extraction, the half-finished percentage elongation of synthetic leather is 2～5%.
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| CN1570267A (en) * | 2004-04-26 | 2005-01-26 | 昌邑同大海岛新材料有限公司 | Process for making high simulation ultra-fine fabric leather based cloth |
| US20060272770A1 (en) * | 2004-08-24 | 2006-12-07 | San Fang Chemical Industry Co., Ltd. | Method for making artificial leather with superficial texture |
| CN102234937A (en) * | 2010-05-07 | 2011-11-09 | 福建兰峰制革有限公司 | Production process of top layer leather-simulated super-fibre synthetic leather |
| CN102071495B (en) * | 2010-07-28 | 2015-06-17 | 烟台万华超纤股份有限公司 | Figured sea-island super-fine fiber, and preparation method thereof and synthetic leather preparing process method using same |
| CN102304858B (en) * | 2011-07-28 | 2013-02-13 | 山东同大海岛新材料股份有限公司 | Preparation method of superfine fiber high-imitation grain synthetic leather |
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2012
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