CN112111976A - Waterborne polyurethane superfine fiber synthetic leather and preparation method thereof - Google Patents
Waterborne polyurethane superfine fiber synthetic leather and preparation method thereof Download PDFInfo
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- CN112111976A CN112111976A CN201910540282.7A CN201910540282A CN112111976A CN 112111976 A CN112111976 A CN 112111976A CN 201910540282 A CN201910540282 A CN 201910540282A CN 112111976 A CN112111976 A CN 112111976A
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- superfine fiber
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- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
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- 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
- D06N3/0004—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 ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
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- 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
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
- D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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- D06N2205/00—Condition, form or state of the materials
- D06N2205/02—Dispersion
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Abstract
The invention relates to the technical field of synthetic leather preparation, and particularly discloses waterborne polyurethane superfine fiber synthetic leather and a preparation method thereof, wherein the preparation method comprises the step of treating the superfine fiber non-woven fabric with an agar aqueous solution before dipping the superfine fiber non-woven fabric in waterborne polyurethane slurry, and utilizes the characteristic that the difference between the agar solidifying point (40 ℃) and the melting point (95 ℃) is large, the superfine fiber non-woven fabric is dipped in a hot water solution of agar and then cooled until the agar is solidified, the solidified agar is coated on the surface of the superfine fiber, so that the situation that the superfine fiber product is hardened due to the fact that the waterborne polyurethane resin and the fiber are bonded together to limit the free movement between the fibers is prevented to a certain extent, and the synthetic leather product is ensured to have good flexibility and folding resistance; in addition, agar is a hydrophilic colloid extracted from the class Rhodophyceae, which is edible and easily degradable, thereby eliminating the post-treatment step, reducing the production cost and being more environmentally friendly.
Description
Technical Field
The invention relates to the technical field of synthetic leather preparation, and particularly relates to waterborne polyurethane superfine fiber synthetic leather and a preparation method thereof.
Background
The natural leather is mainly classified into pig leather, cow leather, horse leather, donkey leather, kangaroo leather and the like according to the types, and a small amount of fish leather, reptile leather, amphibian leather, ostrich leather and the like are additionally arranged. Along with the development of human beings, the natural leather has a long history, and has the natural characteristics of high strength, natural grains, greasy hand feeling, excellent air permeability and the like, thereby being widely applied to life and production. However, as the population of the world increases, the living standard of people is continuously improved, and the economy of various countries is rapidly developed, the demand of human beings on leather is multiplied, and the animal skin resources are globally deficient, the processing cost is rapidly increased, and the serious environmental pollution causes that the natural leather can not meet the normal demand of people seriously. Therefore, it is necessary to develop artificial leather and synthetic leather to make up for the shortcomings of natural leather.
The superfine fiber synthetic leather is artificial leather following PVC and PU, and is prepared by adopting nylon 6(PA6) superfine fiber with the structure and performance similar to those of a fixed island collagen fiber in natural leather to prepare high-density non-woven fabric with a three-dimensional net structure, filling polyurethane with an open microporous structure and excellent performance, and performing post-processing treatment. The synthetic leather has the inherent hygroscopicity of the figured island superfine collagen fiber natural leather. Therefore, the leather can be compared with high-grade natural leather in terms of internal microstructure, appearance texture, physical properties, wearing comfort and the like. In addition, the superfine fiber synthetic leather is superior to natural leather in chemical resistance, quality uniformity, production and processing adaptability, water resistance, mildew resistance and the like, is used for manufacturing luggage, clothes, shoes, automotive interiors and the like, and has wide development prospect. However, like conventional synthetic leather, superfine fiber synthetic leather must use a large amount of solvent type polyurethane resin and organic solvent as main raw materials, which has a serious impact on the damage of ecological environment, and at the same time, cannot become a real ecological environment-friendly product and has high price, so that the practical application of the superfine fiber synthetic leather must be limited to a certain extent.
Therefore, the prior art discloses a preparation method of waterborne polyurethane superfine fiber synthetic leather, which comprises the steps of dipping superfine fiber non-woven fabric into polyvinyl alcohol aqueous solution for pretreatment; dipping the obtained pretreated superfine fiber non-woven fabric into aqueous polyurethane slurry to obtain a dipped superfine fiber non-woven fabric; the water-based polyurethane superfine fiber synthetic leather is finally obtained by carrying out a series of treatments such as microwave solidification and drying on the impregnated superfine fiber non-woven fabric, although the synthetic leather prepared by the method has the characteristics of soft hand feeling and excellent folding resistance, the microwave power consumption in actual production is too high, the energy consumption is high, and the energy conservation and the environmental protection are not facilitated; in addition, the polyvinyl alcohol has certain toxicity, is a high polymer and is difficult to degrade, and a specific method is required to be adopted for removal treatment in the subsequent process, so that the process complexity is increased, and the production cost is increased.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of high production cost and environmental pollution of the preparation method of the waterborne polyurethane superfine fiber synthetic leather in the prior art, thereby providing the preparation method of the waterborne polyurethane superfine fiber synthetic leather with energy conservation and environmental protection. Meanwhile, the invention also provides the waterborne polyurethane superfine fiber synthetic leather prepared by the preparation method.
In order to solve the technical problems, the invention provides a preparation method of waterborne polyurethane superfine fiber synthetic leather, which comprises the following steps:
dipping the superfine fiber non-woven fabric into the aqueous polyurethane slurry to obtain a dipped superfine fiber non-woven fabric;
drying the impregnated superfine fiber non-woven fabric, and then carrying out alkali washing to open the fiber to obtain superfine fiber base fabric;
carrying out post-treatment on the superfine fiber base cloth to obtain the waterborne polyurethane superfine fiber synthetic leather; wherein,
before the superfine fiber non-woven fabric is soaked in the water-based polyurethane slurry, the method also comprises the step of treating the superfine fiber non-woven fabric with an agar water solution.
Further, the step of treating with an aqueous agar solution comprises the steps of:
and (3) dipping the superfine fiber non-woven fabric into the agar aqueous solution, taking out, removing the agar aqueous solution on the surface, and cooling until the agar is solidified.
Further, the concentration of the agar aqueous solution is 0.3-10 wt%.
Further, the superfine fiber non-woven fabric is island sea superfine fiber with the thickness of 1.0-1.7 mm;
furthermore, the island-in-sea superfine fiber is obtained by melt co-extrusion of PA6 and COPET, and the mass ratio of PA6 to COPET is 7: 3.
Further, the solid content of the aqueous polyurethane slurry is 10-30 wt%, the viscosity is 1000-3000 cps, and the foaming density is 500-800 g/mL; the water-based polyurethane sizing agent comprises the following components in parts by weight based on the total weight of the water-based polyurethane sizing agent: 100 parts of waterborne polyurethane; 1-3 parts of color paste; 1-3 parts of a thickening agent; 2-5 parts of a foaming agent; 2-5 parts of a foam stabilizer; 0.2-1 part of a crosslinking agent.
Further, the aqueous polyurethane is nonionic aqueous polyurethane;
further, the nonionic aqueous polyurethane is aliphatic nonionic aqueous polyurethane.
Further, the method further comprises the step of extruding the impregnated microfiber non-woven fabric before drying the impregnated microfiber non-woven fabric.
Further, the extrusion is gap rolling.
Furthermore, the rolling gap is 0.5-1.7 mm.
Further, the temperature of the drying treatment is 80-100 ℃.
Further, the alkali washing fiber is carried out for 40-60 min under the conditions of 5-10 wt% of sodium hydroxide aqueous solution and 90-100 ℃.
Further, the post-treatment comprises the steps of washing, drying, sanding, veneering and kneading the superfine fiber base fabric in sequence.
The invention also provides the waterborne polyurethane superfine fiber synthetic leather prepared by the preparation method.
In the present invention, the solid content (G) means waterThe mass percentage of the residual part of the dried polyurethane slurry in the total amount is that the resin M with proper weight is taken0Drying in a clean surface dish in an oven at about 80 deg.C, taking off the dry film, and weighing M1，G＝M1/M0X is 100%; the pressure absorption rate is also called liquid carrying rate, namely the mass of liquid in the superfine fiber non-woven fabric accounts for the mass of the empty non-woven fabric after impregnation.
The technical scheme of the invention has the following advantages:
1. the preparation method of the waterborne polyurethane superfine fiber synthetic leather provided by the invention comprises the steps of dipping the superfine fiber non-woven fabric into waterborne polyurethane slurry, and treating the superfine fiber non-woven fabric with agar aqueous solution, wherein the superfine fiber non-woven fabric is dipped into hot water solution of agar by utilizing the characteristic that the difference between the freezing point (40 ℃) and the melting point (95 ℃) of the agar is large, then the superfine fiber non-woven fabric is cooled until the agar is solidified, the solidified agar is coated on the surface of the superfine fiber, and the situation that the waterborne polyurethane resin and the fiber are bonded together to limit the free movement between the fibers to cause the hardening of the superfine fiber product is prevented to a certain extent, so that the synthetic leather product has good flexibility and folding resistance; in addition, agar is a hydrophilic colloid extracted from the class Rhodophyceae, which is edible and easily degradable, thereby eliminating the post-treatment step, reducing the production cost and being more environmentally friendly.
2. The preparation method of the waterborne polyurethane superfine fiber synthetic leather adopts island-shaped sea-island superfine fiber non-woven fabric, the island-shaped sea-island fiber is a composite fiber formed by uniformly embedding a dispersion polymer (island component) in a continuous phase polymer (sea component), and the island component and the sea component are continuously, densely and uniformly distributed on the longitudinal axis of the fiber, so that the strength and the handfeel softness of the superfine fiber synthetic leather product are improved.
3. According to the preparation method of the waterborne polyurethane superfine fiber synthetic leather, waterborne polyurethane is used as a main body, solvent type polyurethane resin is replaced, the problems of volatilization and residue of an organic solvent are avoided, the whole production process is environment-friendly and pollution-free, and real clean production is realized; the viscosity of the aqueous polyurethane slurry is in a reasonable range, so that the superfine fiber non-woven fabric can be wetted, and the hand feeling of the product is not hard and solid. In addition, the aqueous polyurethane slurry has a certain foaming density, so that a plurality of foam holes can be generated in the fiber when the polyurethane resin is solidified, the elasticity of the synthetic leather product is further improved, and the synthetic leather product has better hand feeling.
4. The preparation method of the waterborne polyurethane superfine fiber synthetic leather provided by the invention adopts the nonionic waterborne polyurethane, has excellent chemical properties such as better acid and alkali resistance, yellowing resistance, hydrolysis resistance and the like, also has better softness, plump hand feeling and good resilience, and is beneficial to improving the comprehensive performance of synthetic leather products.
5. The preparation method of the waterborne polyurethane superfine fiber synthetic leather provided by the invention is simple in process, short in solidification time, green and environment-friendly, and suitable for industrial production.
Drawings
FIG. 1 is a GC-MS detection map of formaldehyde in a veneered superfine fiber synthetic leather product of the invention;
FIG. 2 is a GC-MS detection map of DMF in the veneered superfine fiber synthetic leather product of the invention;
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
In the following examples, the nonionic aqueous polyurethane is Vesmody-U905 slurry or Vesmody-U601 slurry of Wanhua chemical Co., Ltd, Nippon China, and the black color paste is 6701 color paste black FBRN of Chihua chemical technology Co., Ltd, Jinan xi, Chihua, China; the foaming agent is sodium alkyl alcohol polyoxyethylene sulfate; the foam stabilizer is fatty acid ethanolamide; the superfine fiber non-woven fabric is island sea superfine fiber and is prepared by mixing, melting and co-extruding PA6 and COPET according to the mass ratio of 7: 3.
Example 1
The embodiment provides waterborne polyurethane superfine fiber synthetic leather, and a preparation method thereof comprises the following steps:
(1) preparation of agar aqueous solution and aqueous polyurethane slurry:
adding a proper amount of agar powder into hot water at 95 ℃, and stirring to fully dissolve the agar powder in the hot water to obtain 0.5 wt% of agar aqueous solution for later use;
taking 100g of Vesmody-U905 slurry with the solid content of 40%, adding 62.5g of deionized water, 2g of black color paste, 5g of foaming agent, 3g of foam stabilizer, 2g of hydroxymethyl cellulose and 0.5g of aziridine crosslinking agent, uniformly stirring, and mechanically foaming to prepare aqueous polyurethane slurry with the foaming density of 650g/L, the viscosity of 1500cps and the solid content of 20 wt% for later use;
(2) soaking a piece of superfine fiber non-woven fabric with the thickness of 1.4mm in the agar aqueous solution, taking out the non-woven fabric after the non-woven fabric is completely soaked, quickly removing the redundant agar aqueous solution on the surface of the non-woven fabric through a rolling mill under full pressure, and then flatly paving the non-woven fabric on a coating platform for waiting for natural cooling and solidification;
(3) dipping the non-woven fabric dipped with the agar aqueous solution in the step (2) into the aqueous polyurethane slurry, taking out the non-woven fabric after the non-woven fabric is completely soaked, quickly passing through a rolling mill roller with an adjusted gap of 0.8mm, removing the excessive aqueous polyurethane slurry on the surface to obtain the dipped superfine fiber non-woven fabric with the pressure absorption rate of about 250%, and then putting the dipped superfine fiber non-woven fabric into an oven at 85 ℃;
(4) placing the impregnated waterborne polyurethane non-woven fabric dried in the step (3) in a NaOH aqueous solution with the temperature of 95 ℃ and the weight percent of 10% for alkali washing and fiber opening for 1h to obtain superfine fiber base fabric;
(5) washing the superfine fiber base cloth with water, and drying in an oven at 120 ℃;
(6) and (4) sanding, veneering and graining the superfine fiber base cloth dried in the step (5) to obtain the waterborne polyurethane superfine fiber synthetic leather.
Example 2
The embodiment provides waterborne polyurethane superfine fiber synthetic leather, and a preparation method thereof comprises the following steps:
(1) preparation of agar aqueous solution and aqueous polyurethane slurry:
adding a proper amount of agar powder into hot water at 95 ℃, and stirring to fully dissolve the agar powder in the hot water to obtain 0.3 wt% of agar aqueous solution for later use;
taking 100g of Vesmody-U905 slurry with the solid content of 40%, adding 150g of deionized water, 2g of black color paste, 6g of foaming agent, 3.5g of foam stabilizer, 2.5g of hydroxymethyl cellulose and 0.5g of aziridine crosslinking agent, uniformly stirring, and mechanically foaming to prepare waterborne polyurethane slurry with the foaming density of 650g/L, the viscosity of 2500cps and the solid content of 21 wt% for later use;
(2) soaking a piece of superfine fiber non-woven fabric with the thickness of 1.4mm in the agar aqueous solution, taking out the non-woven fabric after the non-woven fabric is completely soaked, quickly removing the redundant agar aqueous solution on the surface of the non-woven fabric through a rolling mill under full pressure, and then flatly paving the non-woven fabric on a coating platform for waiting for natural cooling and solidification;
(3) dipping the non-woven fabric dipped with the agar aqueous solution in the step (2) into the aqueous polyurethane slurry, taking out the non-woven fabric after the non-woven fabric is completely soaked, quickly passing through a rolling mill roller with an adjusted gap of 0.8mm, removing the excessive aqueous polyurethane slurry on the surface to obtain the dipped superfine fiber non-woven fabric with the pressure absorption rate of about 250%, and then putting the dipped superfine fiber non-woven fabric into an oven at 85 ℃;
(4) placing the impregnated waterborne polyurethane non-woven fabric dried in the step (3) in a NaOH aqueous solution with the temperature of 95 ℃ and the weight percent of 10% for alkali washing and fiber opening for 1h to obtain superfine fiber base fabric;
(5) washing the superfine fiber base cloth with water, and drying in an oven at 120 ℃;
(6) and (4) sanding, veneering and graining the superfine fiber base cloth dried in the step (5) to obtain the waterborne polyurethane superfine fiber synthetic leather.
Example 3
The embodiment provides waterborne polyurethane superfine fiber synthetic leather, and a preparation method thereof comprises the following steps:
(1) preparation of agar aqueous solution and aqueous polyurethane slurry:
adding a proper amount of agar powder into hot water at 100 ℃, and stirring to fully dissolve the agar powder in the hot water to obtain a 10 wt% agar aqueous solution for later use;
taking 100g of Vesmody-U905 slurry with the solid content of 40%, adding 355g of deionized water, 1g of black color paste, 2g of foaming agent, 2g of foam stabilizer, 1g of hydroxyethyl cellulose and 0.2g of aziridine crosslinking agent, uniformly stirring, and mechanically foaming to prepare aqueous polyurethane slurry with the foaming density of 500g/L, the viscosity of 1000cps and the solid content of 10 wt% for later use;
(2) soaking a piece of superfine fiber non-woven fabric with the thickness of 1.0mm in the agar aqueous solution, taking out the non-woven fabric after the non-woven fabric is completely soaked, quickly removing the redundant agar aqueous solution on the surface of the non-woven fabric through a rolling mill under full pressure, and then flatly paving the non-woven fabric on a coating platform for waiting for natural cooling and solidification;
(3) dipping the non-woven fabric dipped with the agar aqueous solution in the step (2) into the aqueous polyurethane slurry, taking out the non-woven fabric after the non-woven fabric is completely soaked, quickly removing the excessive aqueous polyurethane slurry on the surface through a rolling mill roller with an adjusted gap of 0.5mm to obtain a dipped superfine fiber non-woven fabric with a pressure absorption rate of about 200%, removing the excessive aqueous polyurethane slurry on the surface, and then putting the dipped superfine fiber non-woven fabric into an oven at 80 ℃ for drying;
(4) placing the impregnated waterborne polyurethane non-woven fabric dried in the step (3) in a 10 wt% NaOH aqueous solution at 100 ℃ for alkali washing and fiber opening for 40min to obtain superfine fiber base fabric;
(5) washing the superfine fiber base cloth with water, and drying in an oven at 120 ℃;
(6) and (4) sanding, veneering and graining the superfine fiber base cloth dried in the step (5) to obtain the waterborne polyurethane superfine fiber synthetic leather.
Example 4
The embodiment provides waterborne polyurethane superfine fiber synthetic leather, and a preparation method thereof comprises the following steps:
(1) preparation of agar aqueous solution and aqueous polyurethane slurry:
adding a proper amount of agar powder into hot water at 100 ℃, and stirring to fully dissolve the agar powder in the hot water to obtain a 5 wt% agar aqueous solution for later use;
taking 100g of Vesmody-U601 slurry with the solid content of 35%, adding 55g of deionized water, 3g of black color paste, 5g of foaming agent, 5g of foam stabilizer, 3g of methyl hydroxypropyl cellulose and 1g of aziridine crosslinking agent, uniformly stirring, and mechanically foaming to prepare aqueous polyurethane slurry with the foaming density of 800g/L, the viscosity of 3000cps and the solid content of 30 wt% for later use;
(2) soaking a piece of superfine fiber non-woven fabric with the thickness of 1.7mm in the agar aqueous solution, taking out the non-woven fabric after the non-woven fabric is completely soaked, quickly removing the redundant agar aqueous solution on the surface of the non-woven fabric through a rolling mill under full pressure, and then flatly paving the non-woven fabric on a coating platform for waiting for natural cooling and solidification;
(3) dipping the non-woven fabric dipped with the agar aqueous solution in the step (2) into the aqueous polyurethane slurry, taking out the non-woven fabric after the non-woven fabric is completely soaked, quickly passing through a rolling mill roller with the adjusted gap of 1.7mm, removing the excessive aqueous polyurethane slurry on the surface to obtain the dipped superfine fiber non-woven fabric with the pressure absorption rate of about 300 percent, and then putting the dipped superfine fiber non-woven fabric into an oven at 80 ℃;
(4) placing the impregnated water-based polyurethane non-woven fabric dried in the step (3) in a 5 wt% NaOH aqueous solution at 90 ℃ for alkali-washing and opening for 1h to obtain superfine fiber base fabric;
(5) washing the superfine fiber base cloth with water, and drying in an oven at 120 ℃;
(6) and (4) sanding, veneering and graining the superfine fiber base cloth dried in the step (5) to obtain the waterborne polyurethane superfine fiber synthetic leather.
Comparative example 1
The comparative example provides a waterborne polyurethane superfine fiber synthetic leather, and the preparation method is basically the same as that of example 1, except that the comparative example adopts 0.1 wt% of agar aqueous solution to treat the superfine fiber non-woven fabric.
Comparative example 2
The comparative example provides waterborne polyurethane superfine fiber synthetic leather, and the preparation method is basically the same as that in example 1, except that 15 wt% of agar aqueous solution is adopted to treat superfine fiber non-woven fabric.
Comparative example 3
The comparative example provides a waterborne polyurethane superfine fiber synthetic leather, and the preparation method is basically the same as that in example 1, except that the comparative example does not adopt agar aqueous solution to treat superfine fiber non-woven fabric.
Comparative example 4
The comparative example provides waterborne polyurethane superfine fiber synthetic leather, and the preparation method is basically the same as that in example 1, except that the impregnation solution adopted in the preparation of the superfine fiber base fabric in the comparative example is a waterborne polyurethane solution with solid content of 5 wt%, viscosity of 500cps and foaming density of 650 g/mL.
Comparative example 5
The comparative example provides waterborne polyurethane superfine fiber synthetic leather, and the preparation method is basically the same as that in example 1, except that the impregnation solution adopted in the preparation of the superfine fiber base fabric in the comparative example is a waterborne polyurethane solution with solid content of 50 wt%, viscosity of 3500cps and foaming density of 650 g/mL.
Experimental example 1
The veneered superfine fiber synthetic leather products obtained in examples 1-4 and comparative examples 1-5 were subjected to relevant performance tests according to DIN EN ISO32100 standard, and the results are shown in Table 1.
TABLE 1 Properties of various veneered superfine fiber synthetic leather products
The hydrolysis resistance test is a jungle weather resistance test on the synthetic leather product, and specifically, the microfiber leather product is placed in a high-temperature high-humidity constant-temperature constant-humidity experimental box with the temperature of (70 +/-2) DEG C and the relative humidity of (95 +/-5%), and the synthetic leather product is observed to have changes after 10 weeks.
As can be seen from the above tables, the veneered superfine fiber synthetic leather products of examples 1-4 of the invention have excellent performance in all aspects, soft texture and excellent rebound resilience.
Experimental example 2
The concentrations of formaldehyde and DMF in the veneered superfine fiber synthetic leather product of example 1 of the invention were measured by GC-MS 6800 gas chromatography-mass spectrometer, as shown in fig. 1 and fig. 2 and table 2, respectively.
TABLE 2 concentration of Formaldehyde and DMF in the veneered superfine fiber synthetic leather product of the invention
| Component name | Quantitative ion | Retention time/min | Peak area | Peak height | Sample concentration/ppm |
| Formaldehyde (I) | 210 | 8.96 | 1657 | 1675 | 1.927 |
| DMF | 73 | 5.124 | 183 | 145 | 0.240 |
As can be seen from the data in Table 2 above, the formaldehyde concentration in the product was 1.927ppm and the DMF concentration was 0.240ppm, which completely met the specifications in the standards regarding the residual formaldehyde and DMF levels.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A preparation method of waterborne polyurethane superfine fiber synthetic leather comprises the following steps:
dipping the superfine fiber non-woven fabric into the aqueous polyurethane slurry to obtain a dipped superfine fiber non-woven fabric;
drying the impregnated superfine fiber non-woven fabric, and then carrying out alkali washing to open the fiber to obtain superfine fiber base fabric;
carrying out post-treatment on the superfine fiber base cloth to obtain the waterborne polyurethane superfine fiber synthetic leather; it is characterized in that the preparation method is characterized in that,
before the superfine fiber non-woven fabric is soaked in the water-based polyurethane slurry, the method also comprises the step of treating the superfine fiber non-woven fabric with an agar water solution.
2. The method of claim 1, wherein the step of treating with an aqueous agar solution comprises the steps of:
and (3) dipping the superfine fiber non-woven fabric into the agar aqueous solution, taking out, removing the agar aqueous solution on the surface, and cooling until the agar is solidified.
3. The method according to claim 1 or 2, wherein the concentration of the agar aqueous solution is 0.3 to 10 wt%.
4. The production method according to any one of claims 1 to 3, wherein the ultrafine fiber nonwoven fabric is sea-island ultrafine fiber of island type.
5. The preparation method according to any one of claims 1 to 4, wherein the aqueous polyurethane slurry has a solid content of 10 to 30 wt%, a viscosity of 1000 to 3000cps, and a foaming density of 500 to 800 g/mL;
the water-based polyurethane sizing agent comprises the following components in parts by weight based on the total weight of the water-based polyurethane sizing agent: 100 parts of waterborne polyurethane; 1-3 parts of color paste; 1-3 parts of a thickening agent; 2-5 parts of a foaming agent; 2-5 parts of a foam stabilizer; 0.2-1 part of a crosslinking agent.
6. The method according to claim 5, wherein the aqueous polyurethane is a nonionic aqueous polyurethane.
7. The method according to any one of claims 1 to 6, further comprising a step of subjecting the impregnated ultrafine fiber nonwoven fabric to a pressing treatment before drying the impregnated ultrafine fiber nonwoven fabric.
8. The production method according to any one of claims 1 to 7, wherein the alkali-washing fiber-opening is carried out for 40 to 60 minutes under conditions of 5 to 10 wt% aqueous sodium hydroxide solution and 90 to 100 ℃.
9. The production method according to any one of claims 1 to 8, wherein the post-treatment comprises the steps of washing the ultrafine fiber base fabric with water, drying, sanding, facing and graining in this order.
10. The aqueous polyurethane superfine fiber synthetic leather obtained by the preparation method of the aqueous polyurethane superfine fiber synthetic leather according to any one of claims 1 to 9.
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