CN115584641A - Bio-based TPU/graphene waterborne polyurethane synthetic leather for sports and leisure shoes and preparation method thereof - Google Patents
Bio-based TPU/graphene waterborne polyurethane synthetic leather for sports and leisure shoes and preparation method thereof Download PDFInfo
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 55
- 239000004814 polyurethane Substances 0.000 title claims abstract description 55
- 239000002649 leather substitute Substances 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 58
- 238000000576 coating method Methods 0.000 claims abstract description 58
- 238000005452 bending Methods 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 238000005187 foaming Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 230000002457 bidirectional effect Effects 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 8
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 230000037303 wrinkles Effects 0.000 abstract description 8
- 229920005749 polyurethane resin Polymers 0.000 abstract description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 65
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 65
- 239000000463 material Substances 0.000 description 10
- 238000004383 yellowing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920006926 PFC Polymers 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 5
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 5
- 239000006260 foam Substances 0.000 description 4
- 239000010985 leather Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000013080 microcrystalline material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
- D06N3/0025—Rubber threads; Elastomeric fibres; Stretchable, bulked or crimped fibres; Retractable, crimpable fibres; Shrinking or stretching of fibres during manufacture; Obliquely threaded fabrics
- D06N3/0027—Rubber or elastomeric fibres
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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
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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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
- D06N3/007—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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- 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
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
- D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
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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
- D06N2211/00—Specially adapted uses
- D06N2211/10—Clothing
- D06N2211/106—Footwear
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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
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Abstract
The invention discloses a bio-based TPU/graphene waterborne polyurethane synthetic leather for sports and leisure shoes and a preparation method thereof, wherein the preparation method comprises the following steps: mixing and stirring graphene, a high-efficiency emulsifier and waterborne polyurethane resin to obtain uniform and stable composite slurry; preparing the composite slurry into a foaming coating solution, coating the foaming coating solution on the surface of release paper, and drying by adopting a step drying type full-dry-pasting process until the water content of the coating is 10-15%; the dried coating and the bio-based TPU are attached by a novel guide roller which is a bending roller with a bending radian and bidirectional threads. The waterborne polyurethane composite material prepared by the preparation method has excellent ecological environmental protection property, does not have the problems of shrinkage wrinkles and finished product shrinkage edge warping, and improves the first-class product rate of products.
Description
Technical Field
The invention belongs to the technical field of polyurethane synthetic leather, and particularly relates to a preparation method of bio-based TPU/graphene waterborne polyurethane synthetic leather for sports and leisure shoes, and further relates to polyurethane synthetic leather prepared by the preparation method.
Background
At present, in the technical field of TPU polyurethane synthetic leather, a product produced by adhering petrochemical-based TPU serving as a base material to a solvent-based surface layer is adopted as a traditional material, the raw materials and intermediates come from resources such as petroleum, coal and the like, most of the raw materials and intermediates are chemicals capable of releasing harmful substances, and the product is not ecological and environment-friendly, and is wear-resistant, scratch-resistant, bending-resistant and yellowing-resistant. Replace petrochemical industry base TPU with biological base TPU, can improve polyurethane synthetic leather's ecological environmental protection nature undoubtedly, nevertheless because the thermostability of ecological base TPU substrate is not good, have great elasticity, lead to easy-to-draw shrink fold in process of production for the finished product shrink sticks up the limit seriously, and finished first-class product rate is declined.
Disclosure of Invention
In view of the above, the invention needs to provide a preparation method of a bio-based TPU/graphene waterborne polyurethane synthetic leather for sports and leisure shoes, so that the prepared waterborne polyurethane synthetic leather has excellent ecological environmental protection performance, does not have the problems of shrinkage wrinkles and finished product shrinkage edge warping, and improves the first-class product rate of products.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a bio-based TPU/graphene waterborne polyurethane synthetic leather for sports and leisure shoes, which comprises the following steps:
mixing and stirring graphene, a high-efficiency emulsifier and waterborne polyurethane to obtain uniform and stable composite slurry;
preparing the composite slurry into a foaming coating liquid, coating the foaming coating liquid on the surface of release paper, and drying the release paper by adopting a step drying type full-dry pasting process until the water content of the coating is 10-15%;
the dried coating and the bio-based TPU are attached by a novel guide roller which is a bending roller with a bending radian and bidirectional threads.
In a further scheme, the composite slurry comprises the following components in parts by weight: 5-10 parts of deionized water, 0.5-1 part of graphene, 90-95 parts of waterborne polyurethane and 0.1-0.3 part of high-efficiency emulsifier.
In a further scheme, the rotation speed of mixing and stirring is 1000-1500r/min, and the time is 30-40min.
In a further scheme, the high-efficiency emulsifier is BYK-104.
In a further scheme, the foaming coating liquid is prepared by mixing 90-120 parts of deionized water, 20-40 parts of composite slurry, 1-3 parts of foaming agent and 0-10 parts of water-based color paste according to parts by mass.
In a further scheme, the step drying type full-dry-pasting process is realized by adopting drying ovens with different gradient temperatures, wherein the length of the drying oven with the first gradient is 20-25m, and the temperature is 50-80 ℃; the length of the oven with the second gradient is 20-25m, and the temperature is 80-100 ℃; the oven length of the third gradient is 15-20m, and the temperature is 100-130 ℃.
In a further scheme, the bio-based TPU has a bio-based content of 50% -60%.
Further, the bending radian theta of the bending roller is 160-170 degrees.
The invention further provides the bio-based TPU/graphene waterborne polyurethane synthetic leather for the sports and leisure shoes, which is prepared by the preparation method.
The invention has the following beneficial effects:
according to the invention, the biological base TPU is attached to the coating by adopting the bending roller with the bending radian and the bidirectional screw thread, and as the biological base TPU film is contacted with the screw edge of the rotary screw thread during attachment work, a transverse expansion force is applied to the biological base TPU film by inclining the screw edge so as to achieve the effect of flattening the film; in addition, the guide roller with the bending radian can be in transverse inclined contact with the TPU film when the guide roller rotates, so that the flattening force is large, and the problem of shrinkage and creasing easily occurring in the production process of the bio-based TPU is effectively solved.
In addition, the whole drying process is mild by adopting a step-type drying and full-dry-pasting process, so that the stress of all parts of the bio-based TPU film is uniform, and the condition that the finished product shrinks and the edge is raised is avoided.
The bio-based TPU/graphene waterborne polyurethane synthetic leather for the sports and leisure shoes prepared by the preparation method disclosed by the invention has extremely high product quality.
Drawings
FIG. 1 is a schematic view of a novel guide roller according to a preferred embodiment of the present invention;
FIG. 2 is a schematic view of the curvature of the novel guide roller of FIG. 1;
fig. 3 is a schematic view showing the structure of the smooth straight roll in comparative example 1.
Detailed Description
The following detailed description of the embodiments of the present invention is provided for illustration only and should not be construed as limiting the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention discloses a preparation method of a bio-based TPU/graphene waterborne polyurethane synthetic leather for sports and leisure shoes, which comprises the following steps:
mixing and stirring graphene, a high-efficiency emulsifier and waterborne polyurethane to obtain uniform and stable composite slurry;
preparing the composite slurry into a foaming coating liquid, coating the foaming coating liquid on the surface of release paper, and drying the release paper by adopting a step drying type full-dry pasting process until the water content of the coating is 10-15%;
the dried coating and the bio-based TPU are attached by a novel guide roller which is a bending roller with a bending radian and bidirectional threads.
The invention adopts the bio-based TPU as the base material, and compared with the TPU taking petroleum base as the base material, the carbon footprint of the invention is reduced by more than 20 percent. Meanwhile, graphene and the efficient emulsifying dispersant are added into the waterborne polyurethane resin in a certain proportion, and the graphene particles are fine, have larger surface energy and are easy to agglomerate, so that the graphene particles are not uniformly dispersed in the polyurethane resin.
Meanwhile, aiming at the fact that the bio-based TPU has thermal instability and large flexibility, stretching shrinkage wrinkles and finished product shrinkage edge warping are easy to occur in the production process, and therefore the special novel guide roller is adopted in the preparation method, and the shrinkage wrinkle problem occurring in the production process is effectively solved. Because the bio-based TPU film is lighter and thinner, the bio-based TPU film is longitudinally stretched under the action of tension in production and movement and is very easy to shrink in the transverse direction to generate wrinkles; and the guide roller with the bending radian can also be in transverse inclined contact with the TPU film when the guide roller rotates, so that the flattening force is large, the using effect is obvious, and the problem of shrinkage and creasing in the production process of the bio-based TPU can be effectively solved.
In the coating drying stage, a step drying type full-dry-pasting laminating process is adopted to control the water content in the foaming coating to be 10-15%, so that the problem of finished product shrinkage and edge warping is effectively solved. The drying process that multiple sections of drying equipment correspond to different temperatures and gradually rise to the set target temperature is adopted in the stepped drying and full-dry-pasting process, the whole drying process is mild, and all parts of the coating can be uniformly stressed. The common drying process adopts single drying equipment and sets the target temperature, when a wet TPU film coated with a surface layer enters, water can be rapidly evaporated, and the problem of shrinkage and edge warping are easily caused due to uneven stress.
Further, in the composite slurry, the mass fraction of each component is not particularly limited, and may be selected according to actual conditions, and preferably, in the composite slurry, the mass fraction of the graphene is between 0.5% and 1.0%. More preferably, in some specific embodiments of the present invention, the deionized water is 5 to 10 parts, the graphene is 0.5 to 1 part, the aqueous polyurethane is 90 to 95 parts, and the high-efficiency emulsifier is 0.1 to 0.3 part.
Further, the mixing and stirring parameters of the composite slurry are not particularly limited as long as the formed slurry is uniform and stable, and in some specific embodiments of the invention, the mixing and stirring speed is 1000-1500r/min and the time is 30-40min.
In a further scheme, the high-efficiency emulsifier is BYK-104.
After the composite slurry is prepared, the composite slurry is required to be prepared into a foaming coating liquid, the specific composition of the foaming coating liquid can be adjusted according to the product performance, and in some specific embodiments of the invention, the foaming coating liquid is prepared by mixing 90-120 parts of deionized water, 20-40 parts of composite slurry, 1-3 parts of foaming agent and 0-10 parts of water-based color paste according to the mass parts. It is understood that the selection of the foaming agent, the aqueous color paste and other additives are conventional in the art and will not be described in detail herein.
Further, in a typical embodiment of the present invention, the step drying type full dry pasting process is implemented by using ovens with different gradient temperatures, wherein the oven length of the first gradient is 20-25m, and the temperature is 50-80 ℃; the length of the oven with the second gradient is 20-25m, and the temperature is 80-100 ℃; the oven length of the third gradient is 15-20m, and the temperature is 100-130 ℃.
In a further aspect, generally, the higher the bio-based content is, the more excellent the environmental protection performance is, and in the case of having all the mechanical properties, it is preferable that the bio-based content of the bio-based TPU is 50% to 60% (by mass).
In a further scheme, the bending radian theta of the bending roller is preferably not less than 160 degrees, because if the bending radian is too small, the contact force difference between the middle part and two ends of the bio-based TPU film and the roller is large, the bio-based TPU film is deformed due to uneven stress. For the above reasons and in order to ensure that the lateral oblique contact angle with the bio-based TPU film is sufficiently large when the roll is rotated and ensure sufficient lateral spreading force, it is preferable that the bending curvature θ of the bending roll is 160 to 170 °.
The invention provides a bio-based TPU/graphene waterborne polyurethane synthetic leather for sports and leisure shoes, which is prepared by the preparation method.
The present invention is illustrated below by specific examples, which are provided for illustrative purposes only and do not limit the scope of the present invention in any way, and in addition, unless otherwise specified, conditions or steps are not described in detail and the methods are conventional, and reagents and materials used are commercially available.
The reagent information used in the following examples and comparative examples is specifically as follows:
graphene, combined-fertilizer microcrystalline materials science and technology limited;
waterborne polyurethane, tabacco Wanhua chemistry;
high efficiency emulsifier, number BYK-104, BYK, germany;
foaming agent, tabacco Wanhua chemistry;
water-based color paste, zhejiang dark blue New Material science and technology, inc.;
biobased TPU, three companies in korea.
Example 1
Obtaining the graphene/waterborne polyurethane composite slurry
Adding 0.5 part of graphene, 0.1 part of efficient emulsifier BYK-104 and 5 parts of deionized water into 95 parts of waterborne polyurethane, slowly and uniformly stirring for 30min, wherein the rotating speed of a stirring rotor is 1000rpm, and finally preparing uniform and stable composite slurry.
Preparation ofFoaming coating liquid
And preparing 20 parts of composite slurry, 100 parts of deionized water, 1 part of foaming agent and 1 part of aqueous color paste to form the foaming coating liquid.
Preparation of TPU polyurethane synthetic leather
Coating foaming coating liquid on the surface of release paper, adopting the laminating process of the full dry-paste of ladder drying formula to slowly dry, controlling the water content of the foaming coating to be 10%, wherein, different temperature gradient oven temperatures are: the length of the oven with the first gradient is 20 meters, and the temperature is 50 ℃; the length of the oven with the second gradient is 20 meters, and the temperature is 80 ℃; the length of the oven with the third gradient is 15 meters, and the temperature is 120 ℃;
the coating dried by the full dry pasting process is pasted with a bio-based TPU base material, a novel guide roller (the bending radian theta is 160 degrees) shown in figure 2 is fed into the pasting position, so that the pasted product can be continuously produced to be uniform, the surface of the product is stretched and flat, and the product is uniform and free of wrinkles, and the TPU polyurethane synthetic leather is prepared.
The TPU polyurethane synthetic leather is tested to have the abrasion resistance (H-22X 1 KG) of 2000 times; shrinkage of 0.8% (70 ℃ C. 1H); bending for 16 ten thousand times at normal temperature; the height of the raised edge is 0.8cm; yellowing resistance grade 4. The polyurethane leather does not contain perfluorooctanoic acid (PFCs, PFOS) and DMF FREE, has excellent environmental protection performance, and meets the requirements of TPU polyurethane synthetic leather for sports and leisure shoes.
The test reference standards are respectively as follows: measuring the folding fastness of QB/T2714-2005 leather in physical and mechanical tests; measuring yellowing resistance of the QB/T4672-2014 artificial leather synthetic leather test method; QBT2726-2005 leather physical and mechanical test determination of abrasion resistance.
Example 2
Obtaining the graphene/waterborne polyurethane composite slurry
Adding 0.8 part of graphene, 0.3 part of high-efficiency emulsifier BYK-104 and 7 parts of deionized water into 93 parts of waterborne polyurethane, slowly and uniformly stirring for 35min, wherein the rotating speed of a stirring rotor is 1200rpm, and finally preparing uniform and stable composite slurry.
Preparation of a foam coating liquid
And preparing 18 parts of composite slurry, 90 parts of deionized water, 1.5 parts of foaming agent and 1.5 parts of aqueous color paste to form the foaming coating liquid.
Preparation of TPU polyurethane synthetic leather
Coating foaming coating liquid on the surface of release paper, adopting the laminating process of the full dry-paste of ladder drying formula to slowly dry, controlling the water content of the foaming coating to be 12%, wherein, different temperature gradient oven temperatures are: the length of the oven with the first gradient is 20 meters, and the temperature is 60 ℃; the length of the oven with the second gradient is 25 meters, and the temperature is 90 ℃; the length of the oven with the third gradient is 20 meters, and the temperature is 110 ℃;
the coating dried by the full dry pasting process is pasted with a bio-based TPU base material, a novel guide roller (the bending radian theta is 165 degrees) shown in figure 2 is fed into the pasting position, so that the pasted product can be continuously produced to be uniform, the surface of the product is stretched and flat, and the product is uniform and free of wrinkles, and the TPU polyurethane synthetic leather is prepared.
The TPU polyurethane synthetic leather is tested to have the wear resistance (H-22X 1 KG) 2600 times; shrinkage of 0.6% (70 ℃ C. 1H); bending for 18 ten thousand times at normal temperature; the height of the raised edge is 0.6cm; yellowing resistance of 4.5 grade. Does not contain perfluorooctanoic acid (PFCs, PFOS) and DMF FREE, and has excellent environmental protection performance. The requirements of TPU polyurethane synthetic leather for sports and leisure shoes are met.
Example 3
Obtaining graphene/waterborne polyurethane composite slurry
Adding 1 part of graphene, 0.3 part of high-efficiency emulsifier BYK-104 and 10 parts of deionized water into 90 parts of waterborne polyurethane, slowly and uniformly stirring for 40min, wherein the rotating speed of a stirring rotor is 1500rpm, and finally preparing uniform and stable composite slurry.
Preparation of a foam coating liquid
And preparing 25 parts of composite slurry, 110 parts of deionized water, 2 parts of foaming agent and 2 parts of aqueous color paste to form the foaming coating liquid.
Preparation of TPU polyurethane synthetic leather
Coating foaming coating liquid on the surface of release paper, adopting the laminating process of the full dry paste of ladder drying type to slowly dry, controlling the water content of the foaming coating to be 10%, wherein, different temperature gradient oven temperatures are: the length of the oven with the first gradient is 25 meters, and the temperature is 50 ℃; the length of the oven with the second gradient is 20 meters, and the temperature is 80 ℃; the oven length of the third gradient is 20 meters, and the temperature is 130 ℃;
the coating dried by the full dry pasting process is pasted with a bio-based TPU base material, a novel guide roller (the bending radian theta is 170 degrees) shown in figure 2 is fed into the pasting position, so that the pasted product can be continuously produced to be uniform, the surface of the product is stretched and flat, and the product is uniform and free of wrinkles, and the TPU polyurethane synthetic leather is prepared.
The TPU polyurethane synthetic leather is tested to have 3000 times of abrasion resistance (H-22X 1 KG); shrinkage of 0.5% (70 ℃ C. 1H); bending for 15 ten thousand times at normal temperature; the edge is warped by 0.5cm; yellowing resistance of 4.5 grade. Does not contain perfluorooctanoic acid (PFCs, PFOS) and DMF FREE, and has excellent environmental protection performance. The TPU polyurethane synthetic leather requirements for sports and leisure shoes are met.
Comparative example 1
This comparative example uses the same embodiment as example 3 except that: the guide roller for bonding is a common smooth guide roller shown in figure 3, and comprises the following specific steps:
obtaining the graphene/waterborne polyurethane composite slurry
The same as in example 3.
Preparation of a foam coating liquid
The same as in example 3.
Preparation of TPU polyurethane synthetic leather
Coating foaming coating liquid on the surface of release paper, adopting the laminating process of the full dry-paste of ladder drying formula to slowly dry, controlling the water content of the foaming coating to be 10%, wherein, different temperature gradient oven temperatures are: the length of the oven with the first gradient is 25 meters, and the temperature is 50 ℃; the length of the oven with the second gradient is 20 meters, and the temperature is 80 ℃; the oven length of the third gradient is 20 meters, and the temperature is 130 ℃;
and (3) attaching the coating dried by the full dry attaching process to a bio-based TPU (thermoplastic polyurethane) base material, and feeding a common smooth guide roller shown in figure 3 into the attached part to prepare the TPU polyurethane synthetic leather, wherein the TPU film product has serious shrinkage.
The TPU polyurethane synthetic leather passes the test, and the abrasion resistance (H-22 x 1 KG) is 3000 times; shrinkage of 3% (70 ℃ C. 1H); bending for 15 ten thousand times at normal temperature; the height of the raised edge is up to 1.0cm; yellowing resistance of 4.5 grade. Does not contain perfluorooctanoic acid (PFCs, PFOS) and DMF FREE, and has excellent environmental protection performance. The TPU polyurethane synthetic leather has large shrinkage rate and obvious folds, and can not meet the use requirements of the TPU polyurethane synthetic leather for sports and leisure shoes in subsequent processing.
Comparative example 2
This comparative example uses the same embodiment as example 3, except that: coating the foaming coating liquid on the surface of release paper, and drying without adopting a stepped drying and full-dry-pasting mode, wherein the method comprises the following specific steps:
obtaining the graphene/waterborne polyurethane composite slurry
The same as in example 3.
Preparation of a foam coating liquid
The same as in example 3.
Preparation of TPU polyurethane synthetic leather
Coating the foaming coating liquid on the surface of release paper, and adopting a common drying process, wherein the temperature is 130 ℃ and the length is 50m, so that after the TPU film coated with the surface layer enters an oven, the moisture can be rapidly evaporated, and the problem of shrinkage and edge warping is caused by uneven stress of the TPU film;
and (3) attaching the dried coating to a bio-based TPU substrate, and feeding a novel guide roller (the bending radian theta is 170 degrees) shown in figure 2 into the attached part to prepare the TPU polyurethane synthetic leather.
The TPU polyurethane synthetic leather is tested to have 3000 times of abrasion resistance (H-22 x 1 KG); shrinkage of 0.8% (70 ℃ C. 1H); bending for 15 ten thousand times at normal temperature; the raised edge is 4cm; yellowing resistance of 4.5 grade. The environment-friendly performance is superior without perfluorooctanoic acid (PFCs, PFOS) and DMF FREE. But the raised edges are serious, and the use requirements of the TPU polyurethane synthetic leather for sports and leisure shoes for subsequent processing cannot be met.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A preparation method of a bio-based TPU/graphene waterborne polyurethane synthetic leather for sports and leisure shoes is characterized by comprising the following steps:
mixing and stirring graphene, a high-efficiency emulsifier and waterborne polyurethane to obtain uniform and stable composite slurry;
preparing the composite slurry into a foaming coating liquid, coating the foaming coating liquid on the surface of release paper, and drying the release paper by adopting a step drying type full-dry pasting process until the water content of the coating is 10-15%;
the dried coating and the bio-based TPU are attached by a novel guide roller which is a bending roller with a bending radian and bidirectional threads.
2. The preparation method according to claim 1, wherein the composite slurry comprises the following components in parts by mass: 5-10 parts of deionized water, 0.5-1 part of graphene, 90-95 parts of waterborne polyurethane and 0.1-0.3 part of efficient emulsifier.
3. The method of claim 1, wherein the mixing is performed at a speed of 1000 to 1500rpm for 30 to 40min.
4. The method according to any one of claims 1 to 3, wherein the high potency emulsifier is BYK-104.
5. The preparation method of claim 1, wherein the foaming coating liquid is prepared by mixing 90-120 parts of deionized water, 20-40 parts of composite slurry, 1-3 parts of foaming agent and 0-10 parts of water-based color paste according to parts by mass.
6. The preparation method of claim 1, wherein the step drying type full dry pasting process is realized by adopting ovens with different gradient temperatures, wherein the oven length of the first gradient is 20-25m, and the temperature is 50-80 ℃; the length of the oven with the second gradient is 20-25m, and the temperature is 80-100 ℃; the oven length of the third gradient is 15-20m, and the temperature is 100-130 ℃.
7. The method of claim 1, wherein the biobased TPU has a biobased content of 50% to 60%.
8. The method of claim 1, wherein the bending roll has a bending arc θ of 160 ° to 170 °.
9. The bio-based TPU/graphene waterborne polyurethane synthetic leather for sports and leisure shoes is characterized by being prepared by the preparation method according to any one of claims 1 to 8.
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