CN115787316B - High-performance crease-free polyurethane synthetic leather and preparation method and application thereof - Google Patents
High-performance crease-free polyurethane synthetic leather and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-performance crease-free polyurethane synthetic leather and a preparation method and application thereof, wherein the base cloth is subjected to spray filling treatment by using aqueous spray slurry, so that the softness of the original base material is changed, the fuzzing length is controlled, and the defect of poor air permeability and weak crease resistance of the high-performance crease-free polyurethane synthetic leather is overcome on the basis of inheriting the softness, comfort and strong leather texture of a microfiber material, and the high-performance crease-free polyurethane synthetic leather has the characteristics of excellent air permeability, soft texture, crease-free property, light weight and the like; and then the polyurethane material with specific properties is used in the middle layer and the bonding layer to prepare the high-strength crease-free polyurethane synthetic leather material applied to the sports shoes. The material still keeps a good surface effect under the test of 80 ten thousand times of deflection at normal temperature and 20 ten thousand times of deflection at-20 ℃, has excellent wear resistance and deflection resistance, is not easy to deform and damage, and can meet the requirements of the sports shoe market on the excellent functionality and high-strength physical properties of polyurethane synthetic leather products.
Description
Technical Field
The invention belongs to the field of high polymer materials, relates to a high-performance crease-free polyurethane synthetic leather material for shoes, and in particular relates to high-performance crease-free polyurethane synthetic leather, and a preparation method and application thereof.
Background
The traditional polyurethane synthetic leather has stiff hand feeling and poor comfort level in appearance, and the manufactured sports shoes have unrecoverable folds after a period of sports, so that the attractiveness and the comfort level are affected; due to poor wear resistance and durability in physical properties, when the use condition is severe, especially in winter low-temperature environment, the long-term movement bending position is easy to generate the problems of cracks, grinding and the like, and cannot be repaired. The traditional microfiber and dermis materials cannot meet the requirements of ventilation, lightness, thinness, comfort and the like of the sports shoes. Therefore, the market lacks a material which can ensure the wear resistance and the bending resistance of the shoe upper and maintain the crease-free appearance of the shoe upper and can provide comfortable, light, thin and breathable experience for consumers.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the high-performance crease-free polyurethane synthetic leather, the preparation method and the application thereof, and the invention has the characteristics of excellent crease resistance, crease free, ventilation, light weight and the like on the basis of keeping softness and comfort of a microfiber material by modifying the traditional polyurethane synthetic leather, and simultaneously maintains a good surface effect under the test of 80 ten-thousand times of flexure at normal temperature and 20 ten-thousand times of flexure at-20 ℃ so that the polyurethane synthetic leather has excellent wear resistance and flexure resistance, is not easy to deform and damage, and can meet the requirements of sports shoe markets on functional shoes and high-strength physical properties of the traditional polyurethane synthetic leather products.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the first aim of the invention is to provide high-performance crease-free polyurethane synthetic leather, which sequentially comprises a surface layer, a first middle layer, a second middle layer, an adhesive layer and modified base cloth from top to bottom; wherein:
the surface layer is prepared from the following surface layer slurry consisting of the following components in parts by weight: 10-120 parts of polyurethane resin, 50-80 parts of N, N-dimethylformamide, 0.25-0.45 part of flatting agent and 5-15 parts of color paste;
the first interlayer is prepared from the following first interlayer slurry consisting of the following components in parts by weight: 80-130 parts of polyurethane resin, 40-60 parts of N, N-dimethylformamide and 5-15 parts of color paste;
the second interlayer is prepared from the following second interlayer slurry consisting of the following components in parts by weight: 90-130 parts of block polyether polyurethane and 30-50 parts of N, N-dimethylformamide; the method for synthesizing the block polyether polyurethane comprises the following steps: polyethylene glycol and epoxy resin are used as raw materials, and polymerization reaction is carried out for 4-6 hours at the temperature of 80-100 ℃ to prepare the epoxy resin;
the bonding layer is prepared from the following bonding layer slurry consisting of the following components in parts by weight: 90-100 parts of polyester polyol and 80-90 parts of isocyanic acid prepolymer; the polyester polyol and the isocyanic acid prepolymer can rapidly undergo a crosslinking reaction to generate high-viscosity curing to form an adhesive layer; the bonding layer of the invention does not contain organic solvent, and has the advantages of no solvent and environmental protection.
The surface of the modified base cloth is sprayed with water-based spraying filler, and the water-based spraying filler is prepared from the following water-based spraying slurry consisting of the following components in parts by weight: 20-30 parts of waterborne polyurethane, 10-12 parts of pulp powder, 70-90 parts of water and 3 parts of softener. Further preferably, the aqueous polyurethane in the aqueous spraying slurry is XCVB-6313, and XCVB-6313 is a linear high polymer aqueous emulsion obtained by reacting binary isocyanic acid with dihydric alcohol; the paper pulp powder is superfine paper pulp powder, the passing rate of the paper pulp powder through 400 meshes is more than 90%, and the softening agent is LK-156; the spraying method is to spray and fill the base cloth with the aqueous spraying slurry through a large-aperture spraying process, so that the slurry can be controllably and uniformly filled into the gaps of the fluffed surface of the base cloth, and the porosity of the base cloth is reduced.
The second object of the present invention is to provide a method for preparing the high-performance crease-free polyurethane synthetic leather, comprising the following steps:
(1) Mixing water-based polyurethane, water, paper pulp powder and a softening agent to obtain water-based spraying slurry, spraying and filling the base cloth by using the water-based spraying slurry, and drying at 130-140 ℃ to obtain modified base cloth;
(2) Coating the surface layer slurry on the surface of release paper, and drying to obtain a surface layer; preferably, the gap between the cutter heads coated by the surface layer sizing agent is 14-16 filaments, and the drying temperature is 110-120 ℃;
(3) Coating the surface of the surface layer in the step (2) with first intermediate layer slurry, and drying to obtain a first intermediate layer; preferably, the cutter head gap coated by the first middle layer slurry is 23-25 filaments, and the drying temperature is 130-135 ℃;
(4) Coating a second interlayer slurry on the surface of the first interlayer in the step (3), and drying to obtain a second interlayer; preferably, the cutter head gap coated by the second intermediate layer slurry is 25-28 filaments, and the drying temperature is 80-120 ℃.
(5) And (3) coating adhesive layer slurry on the surface of the second intermediate layer in the step (4) to form an adhesive layer, attaching the modified base cloth prepared in the step (1) on the adhesive layer, and heating, drying and naturally curing at normal temperature to obtain the polyurethane synthetic leather material. Preferably, the gap between the cutter heads coated by the adhesive layer slurry is 15-18 filaments, and the drying temperature is 135-140 ℃.
A third object of the present invention is to provide the use of a high performance crease-free polyurethane synthetic leather as described in the first object as a raw material in the preparation of sports shoes.
Compared with the prior art, the invention has the beneficial effects that:
1. the aqueous spraying slurry prepared by the invention contains aqueous polyurethane XCVB-6313 and superfine paper pulp powder, and the aqueous spraying slurry is used for spraying and filling the base cloth through a large-aperture spraying process, so that the slurry can be controllably and uniformly filled into gaps of the fluffy surface of the base cloth, and the porosity of the base cloth is reduced; meanwhile, as the superfine fibers in the pulp powder are filled, the base cloth is endowed with soft and fine handfeel; the uniform and controllable filling reduces the surface tension between the spraying slurry and the base cloth, increases the affinity between the base cloth and the spraying slurry, and ensures that the finished product has the characteristics of soft hand feeling, folding resistance, bending resistance and the like.
2. The invention uses the block polyether resin as the reaction raw material of the second intermediate layer resin, and the polyether resin has good hydrophilicity and rebound resilience in structure; the linear multi-block polyurethane with the shape memory function is obtained by utilizing polyether HO-OH long chain to generate prepolymer and then reacting, so that the flexibility of the synthetic leather material is greatly improved, the synthetic leather material has the function of self-repairing after bending, and the appearance effect of no crease is achieved.
3. The invention uses polyester polyol and isocyanic acid prepolymer to determine the optimal ratio, and rapidly generates crosslinking reaction to generate high viscosity to solidify and form an adhesive layer, and the adhesive layer is used as specific resin to form high-strength bonding with block polyether polyurethane in the second intermediate layer, thus obviously improving the bending strength of the final product. In addition, the high polymer elastomer material formed by the reaction of the polyester polyol and the isocyanic acid prepolymer also has the characteristic of micro-foaming performance, and the base cloth after the wet treatment is reserved after the surface is pasted, so that the light weight, the thinness and the air permeability of the base cloth base material are improved to a certain extent, and the final synthetic leather material has excellent air permeability and simultaneously realizes light weight.
Detailed Description
The present invention will be further described with reference to examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it. In the description of the present invention, it should be understood that the terms "first" and "second" do not denote a particular quantity or order, but rather are used for distinguishing between names.
In addition, the preparation processes in the following examples are conventional means in the art unless specifically described, and therefore, will not be described in detail; the parts in the following embodiments refer to parts by weight.
The block polyether urethanes used in the following examples were synthesized as follows: mixing polyethylene glycol (Shanghai Jiachen chemical industry) and CYD-128 epoxy resin (Shanghai resin factory) according to a mass ratio of 1:2, adding boron trifluoride as a catalyst, and controlling the temperature in a reaction kettle to be about 90 ℃ for reaction for 5.5 hours to obtain the modified polyethylene glycol.
It was found that the ratio of the polyester polyol to the isocyanate prepolymer in the adhesive layer slurry has an effect on the peel strength of the final product, and when the adhesive layer slurry is prepared, the polyester polyol: the isocyanate prepolymers were mixed in weight ratios of 1:1, 10:9, 10:8, 10:7, 10:6, 10:5, and when tested for peel strength, the polyester polyols were found to: when the ratio of the isocyanate to the prepolymer is 10:9, the obtained product has optimal performance. When the amounts of these two substances are more or less than 10:9, the peel strength of the obtained product will be at different levels, and therefore, the polyester polyol will be used in the following examples: the ratio of the prepolymerization of the isocyanate was controlled to be 10:9.
Example 1
In this example, the components, amounts of components, and manufacturer sources of components of the surface layer slurry, the first intermediate layer slurry, the second intermediate layer slurry, the adhesive layer slurry, and the modified base cloth treatment spray slurry are shown in table 1.
TABLE 1
The preparation method of the high-performance crease-free polyurethane synthetic leather in the embodiment is as follows:
a. spraying the 0.8mm panne cloth with water-based spray paint, wherein the speed is 8m/min, and the temperature of the oven is set to 115 ℃ to obtain modified base cloth;
b. coating surface layer slurry on the surface of release paper, wherein the coating gap of a cutter head is 15 wires, and heating and drying at 120 ℃ to form a polyurethane surface layer coating;
c. coating the first intermediate layer slurry on the surface of the surface layer, setting the coating gap of the cutter head to be 25 wires, and heating and drying at 130 ℃ to form a first intermediate layer;
d. coating the second intermediate layer slurry on the surface of the first intermediate layer, wherein the coating gap of the cutter head is 28 filaments, and heating and drying at 110 ℃ to form a second intermediate layer;
e. and (3) defoaming the bonding layer slurry by using a vacuum machine, coating the defoamed bonding layer slurry on the surface of the second intermediate layer, attaching the modified base cloth on the bonding layer, coating 15 wires on a cutter head, heating and drying at 140 ℃, and naturally curing for 40min at normal temperature to obtain the polyurethane synthetic leather material.
Example 2
The components, component amounts and manufacturer sources of the components of the surface layer slurry, the first intermediate layer slurry, the second intermediate layer slurry, the adhesive layer slurry, and the modified base cloth treatment spray coating slurry in this example are shown in table 2.
TABLE 2
The preparation process of the high-performance crease-free polyurethane synthetic leather in the embodiment is as follows:
a. spraying the 0.8mm panne cloth with water-based spray paint, wherein the speed is 10m/min, and the temperature of an oven is set at 125 ℃ to obtain modified base cloth;
b. coating surface layer slurry on the surface of release paper, wherein the coating gap of a cutter head is 15 filaments, and heating and drying the cutter head at 120 ℃ to form a polyurethane surface layer;
c. coating the first intermediate layer slurry on the surface of the surface layer, setting the coating gap of the cutter head to be 25 wires, and heating and drying at 130 ℃ to form a first intermediate layer;
d. coating the second intermediate layer slurry on the surface of the first intermediate layer, wherein the coating gap of the cutter head is 28 filaments, and heating and drying at 110 ℃ to form a second intermediate layer;
e. and (3) defoaming the polyurethane bonding layer slurry by using a vacuum machine, coating the surface of the second intermediate layer with the defoamed polyurethane bonding layer slurry, attaching the modified base cloth on the bonding layer, coating 15 wires with a cutter head coating gap, heating and drying at 135 ℃, and naturally curing for 30min at normal temperature to obtain the polyurethane synthetic leather material.
Example 3
The components, amounts of components and manufacturer sources of components of the surface layer slurry, the first intermediate layer slurry, the second intermediate layer slurry, the adhesive layer slurry, and the modified base cloth treatment spray coating slurry in this example are shown in table 3.
TABLE 3 Table 3
The preparation process of the high-performance crease-free polyurethane synthetic leather in the embodiment is as follows:
a. spraying the 0.8mm panne cloth with water-based spray paint, wherein the speed is 12m/min, and the temperature of an oven is set to 135 ℃ to obtain modified base cloth;
b. coating surface layer slurry on the surface of release paper, wherein the coating gap of a cutter head is 15 filaments, and heating and drying the cutter head at 120 ℃ to form a polyurethane surface layer;
c. coating the first intermediate layer slurry on the surface of the surface layer, setting the coating gap of the cutter head to be 25 wires, and heating and drying at 130 ℃ to form a first intermediate layer;
d. coating the second intermediate layer slurry on the surface of the first intermediate layer, wherein the coating gap of the cutter head is 28 filaments, and heating and drying at 110 ℃ to form a second intermediate layer;
e. and (3) defoaming the polyurethane bonding layer slurry by using a vacuum machine, coating the surface of the second intermediate layer with the defoamed polyurethane bonding layer slurry, attaching the modified base cloth on the bonding layer, coating 15 wires on a cutter head, heating and drying at 150 ℃, and naturally curing for 30min at normal temperature to obtain the polyurethane synthetic leather material.
Comparative example 1
The components, amounts of components and manufacturer sources of components used in the surface layer slurry, the first intermediate layer slurry, the second intermediate layer slurry, and the adhesive layer slurry in this example are shown in table 4.
TABLE 4 Table 4
The preparation process of the high-performance crease-free polyurethane synthetic leather in the embodiment is as follows:
a. coating surface layer slurry on the surface of release paper, wherein the coating gap of a cutter head is 15 filaments, and heating and drying the cutter head at 120 ℃ to form a polyurethane surface layer;
b. coating the first intermediate layer slurry on the surface of the surface layer, setting the coating gap of the cutter head to be 25 wires, and heating and drying at 130 ℃ to form a first intermediate layer;
c. coating the second intermediate layer slurry on the surface of the first intermediate layer, wherein the coating gap of the cutter head is 28 filaments, and heating and drying at 110 ℃ to form a second intermediate layer;
d. and (3) defoaming the polyurethane bonding layer slurry by using a vacuum machine, coating the surface of the second intermediate layer with the defoamed polyurethane bonding layer slurry, attaching the modified base cloth on the bonding layer, coating 15 wires on a cutter head, heating and drying at 140 ℃, and naturally curing for 40min at normal temperature to obtain a final product.
Comparative example 2
The components, amounts of components and manufacturer sources of components of the surface layer slurry, the first intermediate layer slurry, the second intermediate layer slurry, the adhesive layer slurry, and the modified base cloth treatment spray coating slurry in this example are shown in table 5.
TABLE 5
The preparation process of the high-performance crease-free polyurethane synthetic leather in the embodiment is as follows:
a. spraying the 0.8mm panne cloth with water-based spray paint, wherein the speed is 8m/min, and the temperature of the oven is set to 115 ℃ to obtain modified base cloth;
b. coating surface layer slurry on the surface of release paper, wherein the coating gap of a cutter head is 15 filaments, and heating and drying the cutter head at 120 ℃ to form a polyurethane surface layer;
c. coating the first intermediate layer slurry on the surface of the surface layer, setting the coating gap of the cutter head to be 25 wires, and heating and drying at 130 ℃ to form a first intermediate layer;
d. coating the second intermediate layer slurry on the surface of the first intermediate layer, wherein the coating gap of the cutter head is 28 filaments, and heating and drying at 110 ℃ to form a second intermediate layer;
e. and (3) defoaming the polyurethane bonding layer slurry by using a vacuum machine, coating the surface of the second intermediate layer with the defoamed polyurethane bonding layer slurry, attaching the modified base cloth on the bonding layer, coating 15 wires on a cutter head, heating and drying at 140 ℃, and naturally curing for 40min at normal temperature to obtain a final product.
Comparative example 3
The components, amounts of components and manufacturer sources of components of the surface layer slurry, the first intermediate layer slurry, the second intermediate layer slurry, the adhesive layer slurry, and the modified base cloth treatment spray coating slurry in this example are shown in table 6.
TABLE 6
The preparation process of the high-performance crease-free polyurethane synthetic leather in the embodiment is as follows:
a. spraying the 0.8mm panne cloth with water-based spray paint, wherein the speed is 8m/min, and the temperature of the oven is set to 115 ℃ to obtain modified base cloth;
b. coating surface layer slurry on the surface of release paper, wherein the coating gap of a cutter head is 15 filaments, and heating and drying the cutter head at 120 ℃ to form a polyurethane surface layer;
c. coating the first intermediate layer slurry on the surface of the surface layer, setting the coating gap of the cutter head to be 25 wires, and heating and drying at 130 ℃ to form a first intermediate layer;
d. coating the second intermediate layer slurry on the surface of the first intermediate layer, wherein the coating gap of the cutter head is 28 filaments, and heating and drying at 110 ℃ to form a second intermediate layer;
e. and coating the polyurethane bonding layer slurry on the surface of the second intermediate layer, attaching the pretreated synthetic leather base cloth on the bonding layer, coating 15 wires on the cutter head, and heating and drying at 140 ℃ to obtain the final product.
Comparative example 4
The components, amounts of components and manufacturer sources of components used in the face layer slurry, the first intermediate layer slurry, the second intermediate layer slurry, and the adhesive layer slurry in this example are shown in table 7.
TABLE 7
The preparation process of the high-performance crease-free polyurethane synthetic leather in the embodiment is as follows:
a. coating surface layer slurry on the surface of release paper, wherein the coating gap of a cutter head is 15 filaments, and heating and drying the cutter head at 120 ℃ to form a polyurethane surface layer;
b. coating the first intermediate layer slurry on the surface of the surface layer, setting the coating gap of the cutter head to be 25 wires, and heating and drying at 130 ℃ to form a first intermediate layer;
c. coating the second intermediate layer slurry on the surface of the first intermediate layer, wherein the coating gap of the cutter head is 28 filaments, and heating and drying at 110 ℃ to form a second intermediate layer;
d. and coating the surface of the second intermediate layer with polyurethane adhesive layer slurry, attaching normal base cloth on the adhesive layer, setting 15 wires in a cutter head coating gap, and heating and drying at 130 ℃ to obtain a final finished product.
The high performance crease-free polyurethane synthetic leather prepared in examples 1 to 3 and comparative examples 1 to 4 was subjected to a correlation test, and the test results are shown in table 8:
TABLE 8
As can be seen from the test results in Table 8, the comparison between the high molecular polyurethane synthetic leather prepared in examples 1 to 3 and the normal synthetic leather shows that the polyurethane synthetic leather product has the characteristics of high wear resistance, bending resistance, difficult deformation and damage, excellent crease resistance, no crease, ventilation, light weight and the like, has softer hand feeling and more comfortable use feeling, and can meet the requirements of the sports shoe market on functional shoes and high-strength physical properties of the traditional polyurethane synthetic leather product by using the block polyether resin intermediate layer in the modified base cloth and the second intermediate layer and combining the solvent-free bonding layer process
It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (10)
1. A high-performance crease-free polyurethane synthetic leather is characterized in that: the surface layer, the first middle layer, the second middle layer, the bonding layer and the modified base cloth are sequentially included from top to bottom; wherein:
the second interlayer is prepared from the following second interlayer slurry consisting of the following components in parts by weight: 90-130 parts of block polyether polyurethane,N,N30-50 parts of dimethylformamide; the method for synthesizing the block polyether polyurethane comprises the following steps: the preparation method comprises the steps of taking polyethylene glycol and epoxy resin as raw materials, and carrying out polymerization reaction at the temperature of 80-100 ℃ to prepare the epoxy resin;
the bonding layer is prepared from the following bonding layer slurry consisting of the following components in parts by weight: 90-100 parts of polyester polyol and 80-90 parts of isocyanic acid prepolymer;
the surface of the modified base cloth is sprayed with water-based spraying filler, and the water-based spraying filler is prepared from the following water-based spraying slurry consisting of the following components in parts by weight: 20-30 parts of waterborne polyurethane, 10-12 parts of pulp powder, 70-90 parts of water and 3 parts of softener.
2. The high performance crease-free polyurethane synthetic leather of claim 1, wherein: the surface layer is prepared from the following surface layer slurry consisting of the following components in parts by weight:
10-120 parts of polyurethane resin,
N,N50-80 parts of dimethylformamide,
0.25-0.45 part of leveling agent,
5-15 parts of color paste.
3. The high performance crease-free polyurethane synthetic leather of claim 1, wherein: the first interlayer is prepared from the following first interlayer slurry consisting of the following components in parts by weight:
80-130 parts of polyurethane resin,
N,N40-60 parts of dimethylformamide,
5-15 parts of color paste.
4. A method for producing a high-performance crease-free polyurethane synthetic leather according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) Mixing water-based polyurethane, water, paper pulp powder and a softening agent to obtain water-based spraying slurry, spraying, filling and treating the base cloth by using the water-based spraying slurry, and drying to obtain modified base cloth;
(2) Coating the surface layer slurry on the surface of release paper, and drying to obtain a surface layer;
(3) Coating the surface of the surface layer in the step (2) with first intermediate layer slurry, and drying to obtain a first intermediate layer;
(4) Coating a second interlayer slurry on the surface of the first interlayer in the step (3), and drying to obtain a second interlayer;
(5) And (3) coating adhesive layer slurry on the surface of the second intermediate layer in the step (4) to form an adhesive layer, attaching the modified base cloth prepared in the step (1) on the adhesive layer, and heating, drying and naturally curing at normal temperature to obtain the polyurethane synthetic leather material.
5. The method for preparing high-performance crease-free polyurethane synthetic leather according to claim 4, wherein the method comprises the following steps: in the step (1), the drying temperature is 130-140 ℃.
6. The method for preparing high-performance crease-free polyurethane synthetic leather according to claim 4, wherein the method comprises the following steps: in the step (2), the gap between the cutter heads coated by the surface layer slurry is 14-16 filaments, and the drying temperature is 110-120 ℃.
7. The method for preparing high-performance crease-free polyurethane synthetic leather according to claim 4, wherein the method comprises the following steps: in the step (3), the cutter head gap coated by the first intermediate layer slurry is 23-25 filaments, and the drying temperature is 130-135 ℃.
8. The method for preparing high-performance crease-free polyurethane synthetic leather according to claim 4, wherein the method comprises the following steps: in the step (4), the cutter head gap coated by the second intermediate layer slurry is 25-28 filaments, and the drying temperature is 80-120 ℃.
9. The method for preparing high-performance crease-free polyurethane synthetic leather according to claim 4, wherein the method comprises the following steps: in the step (5), the gap between the cutter heads coated with the adhesive layer slurry is 15-18 filaments, and the drying temperature is 135-140 ℃.
10. Use of a high performance crease-free polyurethane synthetic leather according to any of claims 1 to 3 as raw material for the preparation of sports shoes.
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| CN115787316A (en) | 2023-03-14 |
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