CN109762456B - Polyurethane coating for shoe coating and preparation method thereof - Google Patents
Polyurethane coating for shoe coating and preparation method thereof Download PDFInfo
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- CN109762456B CN109762456B CN201910085077.6A CN201910085077A CN109762456B CN 109762456 B CN109762456 B CN 109762456B CN 201910085077 A CN201910085077 A CN 201910085077A CN 109762456 B CN109762456 B CN 109762456B
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Abstract
The invention provides a polyurethane coating for a shoe coating and a preparation method thereof, wherein the preparation method comprises the following steps: step (1): adding isocyanate, polyester polyol, a water removing agent and a diluent into a reaction kettle according to a certain proportion, uniformly stirring, reacting for 6-8 hours at the temperature of 80-120 ℃, removing bubbles in vacuum, and cooling to obtain a component A; step (2): adding polyester polyol, a chain extender, a catalyst and a glycerol solution of dehydrated aluminum potassium sulfate dodecahydrate into a reaction kettle in proportion, uniformly stirring, vacuumizing for 2-3 hours, and removing bubbles to obtain a component B; and (3): and uniformly mixing the component A and the component B according to a ratio, and removing bubbles in vacuum for 30s to obtain the polyurethane coating. The prepared polyurethane coating is used for coating on the surface of a shoe, can be formed at one time, and solves the problem that the reaction of the sprayed polyurethane elastomer and moisture causes bubbles inside the coating.
Description
Technical Field
The invention relates to a polyurethane coating and a preparation method thereof, in particular to a polyurethane coating for a shoe coating and a preparation method thereof.
Background
Conventional articles of footwear generally include two primary elements: the sole is a compact and wear-resistant material and has waterproof performance; the vamp is made of leather or fabric, so that the air permeability is ensured. However, in the conventional shoes, if the height of the sole is too low, water can enter the shoes through the seams and the vamps, the rain boots are shoes used in rainy days, the soles and the vamps of the rain boots are in an integrated mode, the waterproof effect is good, but the vamps are too dense and lose breathability, and are not beneficial to outdoor sports. Therefore, a vamp coating is needed, which can well coat a sole and a part of a vamp, can be waterproof and has good air permeability under the condition of ensuring the wear resistance of the sole, and meanwhile, the material also has good appearance and is convenient for fashionable design.
Polyurethane paint is a common coating at present, but the paint contains a large amount of solvent (organic solvent or water), so that the paint can easily permeate into the interior of textile vamps to cause vamp pollution and lose functionality, and surface sealing treatment is needed to prevent the paint from permeating into the vamps, so that the production efficiency is influenced. In addition, the thickness of the single-pass formed paint is about 20-50 microns, the thickness of 0.2-2.0mm can be achieved only by 10-20 spraying procedures, and each spraying procedure can be carried out only by drying the previous procedure and volatilizing the solvent. This results in extremely low production efficiency. Meanwhile, although the paint can achieve the required transparency and gloss, the wear resistance is extremely poor, and the required wear resistance cannot be achieved.
The polyurethane elastomer for shoe soles has excellent wear resistance, but easily generates a large amount of bubbles due to the characteristic that the polyurethane material itself is easily reacted with moisture. To solve the problem of the polyurethane reacting easily with moisture, the technology of spraying polyurea elastomer was first developed and succeeded by Dudley J.Primeaux II of Huntsman corporation, and the research paper was first published in 1989. In 1991, the technology is put into commercial application in North America, and immediately shows excellent comprehensive performance, so that the technology is popular with users. The technology is applied to high-speed railways, aquatic ponds and swimming venues. The polyurea has the characteristics of strong adhesive force, friction resistance, strong hardness and the like, and is often applied to high-end fields such as spaceflight, ordnance, ships, automobiles and the like; however, the polyurea material is sprayed by a high-pressure sprayer, the reaction speed is too high, and although the polyurea material does not react with moisture in the air, air bubbles trapped in the spraying process cannot escape out of the resin body due to the too high reaction speed, so that many tiny bubbles are formed in the coating layer, and the expected transparent effect cannot be realized. In addition, the aerosol caused by spraying can fall on the surface of the coating to form a plurality of small particle defects, and the grinding and polishing are also needed to achieve the expected effect.
In addition, it is difficult for the conventional polyurethane elastomer to achieve the effect of high transparency and high brightness. The polyurethane elastomer made of polyether is easy to obtain transparent effect, but the performance of the polyurethane elastomer is difficult to meet the wear-resistant effect required by the sole. Polyurethanes made from polyesters have adequate abrasion resistance, but elastomers have inadequate clarity and are difficult to meet with desired requirements.
Therefore, the prior art is in need of improvement.
Disclosure of Invention
The invention aims to provide a polyurethane coating for a shoe coating and a preparation method thereof, and aims to overcome the defects that the existing polyurethane coating has more bubbles and is difficult to realize high transparency.
The technical scheme of the invention is as follows:
a preparation method of a polyurethane coating for shoe coating comprises the following steps:
step (1): adding isocyanate, polyester polyol, a water removing agent and a diluent into a reaction kettle according to a certain proportion, uniformly stirring, reacting for 6-8 hours at the temperature of 80-120 ℃, removing bubbles in vacuum, and cooling to obtain a component A;
step (2): adding polyester polyol, a chain extender, a catalyst and a glycerol solution of dehydrated aluminum potassium sulfate dodecahydrate into a reaction kettle in proportion, uniformly stirring, vacuumizing (-0.095MPa) for 2-3 hours, and removing bubbles to obtain a component B;
and (3): and uniformly mixing the component A and the component B according to a ratio, and removing bubbles in vacuum for 30s to obtain the polyurethane coating.
The preparation method of the polyurethane coating for the shoe coating comprises the following steps of (by weight percentage),
in the step (1), the proportion of isocyanate, polyester polyol, water remover and diluent is as follows: 60-70% of isocyanate, 15-25% of polyester polyol, 1-5% of water removing agent and 5-20% of diluent;
in the step (2), the polyester polyol, the chain extender, the catalyst and the glycerol solution of dehydrated aluminum potassium sulfate dodecahydrate are as follows: 70-85% of polyester polyol, 5-20% of chain extender, 1-3% of catalyst and 8-12% of glycerol solution of dehydrated aluminum potassium sulfate dodecahydrate.
The preparation method of the polyurethane paint for the shoe coating comprises the step (1), wherein the isocyanate is a mixture of 2,4-MDI isomer and 4,4-MDI isomer.
The preparation method of the polyurethane coating for the shoe coating comprises the step (1) of preparing a polyurethane coating for the shoe coating, wherein the water removing agent is a carbodiimide water removing agent.
The preparation method of the polyurethane coating for the shoe coating comprises the step (1) of taking propylene carbonate as a diluent.
The preparation method of the polyurethane coating for the shoe coating comprises the step (2), wherein the chain extender is 1, 4' -butanediol.
The preparation method of the polyurethane coating for the shoe coating comprises the step (2) of using dibutyltin dilaurate as the catalyst.
The preparation method of the polyurethane paint for the shoe coating comprises the step (3), wherein the ratio of the component A to the component B is 1:2-1: 1.
The preparation method of the polyurethane coating for the shoe coating comprises the step of adding dehydrated aluminum potassium sulfate dodecahydrate into glycerol solution of the dehydrated aluminum potassium sulfate dodecahydrate to obtain 5-20% of dehydrated aluminum potassium sulfate dodecahydrate.
Another object of the present invention is to provide a polyurethane coating prepared by the above preparation method.
According to the invention, dehydrated aluminum potassium sulfate dodecahydrate and glycerol are added in the preparation process of the component B, and because the dehydrated aluminum potassium sulfate dodecahydrate and the glycerol have strong water absorbability, the generation of chemical bubbles caused by excessive water in the polyol component can be effectively prevented; dehydrated potassium aluminum sulfate dodecahydrate has strong astringency, and tests prove that the dehydrated potassium aluminum sulfate dodecahydrate is a natural defoaming agent when applied to a polyurethane solvent-free coating system; the glycerol is a natural lubricant, and can remarkably reduce the friction coefficient of a material interface during high-speed stirring in the operation process, thereby playing the role of effectively inhibiting bubbles; in addition, the glycerol (glycerin) is a low molecular alcohol with three functionality degrees, plays a role in optimal heat-sensitive reaction balance in the later stage of thermal reaction in a system, accelerates the curing of the surface of the coating while increasing the internal gel speed, and can effectively improve the working efficiency.
In addition, the catalyst dibutyltin dilaurate selected by the invention can reduce the generation of bubbles to a certain extent.
The polyurethane coating prepared by the invention is used for coating on the surface of a shoe (the sole and part of the vamp can be directly immersed in the polyurethane coating), can be formed once, does not need to be coated again after the previous material is cured, and can be cured and formed for multiple times, so that the complex process of multiple spraying and curing required by using the coating is reduced, and the problem of generating bubbles inside the coating caused by the reaction of the known sprayed polyurethane elastomer and moisture is solved. The coating is cured at normal temperature, saves cost, has no solvent, is low-carbon and environment-friendly, and is transparent and bright.
In addition, the polyurethane coating prepared by the invention can also be used on the surface of a case and bag to perform local coating to improve the comprehensive performance and meet the special requirements of scratch resistance, strong tearing, high peeling strength, water resistance, pollution resistance, antibiosis, skid resistance, beautiful appearance and the like.
The product using the polyurethane coating realizes a novel transparent and bright surface effect, realizes an integral seamless effect, saves the construction cost and greatly improves the production efficiency.
Drawings
FIG. 1 is a photograph of a polyurethane coating prepared in example 1 of the present invention.
FIG. 2 is a photograph of the polyurethane coating prepared in comparative example 1.
FIG. 3 is a photograph of the polyurethane coating prepared in comparative example 2.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
Example 1
The embodiment relates to a preparation method of a polyurethane coating for shoe coating, which comprises the following steps:
step (1): weighing 6kg of isocyanate, 2.5kg of polyester polyol with molecular weight of 2000, 0.1kg of carbodiimide (water remover) and 1.4kg of propylene carbonate (diluent), adding into a reaction kettle, uniformly stirring, reacting for 7 hours at 100 ℃, removing bubbles (-0.095MPa) in vacuum, and cooling to obtain a component A with NCO content of 10.4%;
step (2): weighing 7.0kg of polyester polyol, 2.0kg of 1, 4' -butanediol (chain extender), 0.2kg of dibutyltin dilaurate (catalyst) and 0.8kg of dehydrated aluminum potassium sulfate dodecahydrate glycerol solution, adding the materials into a reaction kettle, uniformly stirring, vacuumizing (-0.095MPa) for 3 hours to remove bubbles to obtain a component B;
and (3): adding 8kg of the component A into 10kg of the component B, uniformly mixing, and removing bubbles in vacuum for 30s to obtain the polyurethane coating (shown in figure 1).
Wherein, in the step (1), the isocyanate is a mixture consisting of 40 percent of 2,4-MDI isomer and 60 percent of 4,4-MDI isomer; in the step (2), the content of dehydrated aluminum potassium sulfate dodecahydrate in the glycerol solution of dehydrated aluminum potassium sulfate dodecahydrate is 15%.
The polyurethane coating prepared in this example was poured onto a flat plate and cured at room temperature to give a clear, bubble-free article.
Example 2
The embodiment relates to a preparation method of a polyurethane coating for shoe coating, which comprises the following steps:
step (1): weighing 7kg of isocyanate, 2.0kg of polyester polyol with molecular weight of 2000, 0.5kg of carbodiimide (water remover) and 0.5kg of propylene carbonate (diluent), adding the materials into a reaction kettle, uniformly stirring, reacting for 7 hours at 90 ℃, removing bubbles (-0.095MPa) in vacuum, and cooling to obtain a component A with NCO content of 21.3%;
step (2): weighing 7.5kg of polyester polyol, 1.0kg of 1, 4' -butanediol (chain extender), 0.3kg of dibutyltin dilaurate (catalyst) and 1.2kg of dehydrated aluminum potassium sulfate dodecahydrate glycerol solution, adding the materials into a reaction kettle, uniformly stirring, vacuumizing (-0.095MPa) for 2 hours to remove bubbles, and obtaining a component B;
and (3): adding 8kg of the component A into 10kg of the component B, uniformly mixing, and removing bubbles in vacuum for 30s to obtain the polyurethane coating.
Wherein, in the step (1), the isocyanate is a mixture consisting of 50 percent of 2,4-MDI isomer and 50 percent of 4,4-MDI isomer; in the step (2), the content of dehydrated potassium aluminum sulfate dodecahydrate in the glycerol solution of dehydrated potassium aluminum sulfate dodecahydrate is 10%.
The polyurethane coating prepared in this example was poured onto a flat plate and cured at room temperature to give a clear, bubble-free article.
Example 3
The embodiment relates to a preparation method of a polyurethane coating for shoe coating, which comprises the following steps:
step (1): weighing 6.5kg of isocyanate, 2.2kg of polyester polyol with molecular weight of 2000, 0.3kg of carbodiimide (water remover) and 1.0kg of propylene carbonate (diluent), adding into a reaction kettle, uniformly stirring, reacting for 8 hours at 80 ℃, removing bubbles (-0.095MPa) in vacuum, and cooling to obtain a component A with NCO content of 16.2%;
step (2): weighing 8.0kg of polyester polyol, 0.9kg of 1, 4' -butanediol (chain extender), 0.1kg of dibutyltin dilaurate (catalyst) and 1.0kg of dehydrated aluminum potassium sulfate dodecahydrate glycerol solution, adding the materials into a reaction kettle, uniformly stirring, vacuumizing (-0.095MPa) for 3 hours to remove bubbles, and obtaining a component B;
and (3): adding 8kg of the component A into 10kg of the component B, uniformly mixing, and removing bubbles in vacuum for 30s to obtain the polyurethane coating.
Wherein, in the step (1), the isocyanate is a mixture consisting of 60 percent of 2,4-MDI isomer and 40 percent of 4,4-MDI isomer; in the step (2), the content of dehydrated aluminum potassium sulfate dodecahydrate in the glycerol solution of dehydrated aluminum potassium sulfate dodecahydrate is 20%.
The polyurethane coating prepared in this example was poured onto a flat plate and cured at room temperature to give a clear, bubble-free article.
Example 4
The embodiment relates to a preparation method of a polyurethane coating for shoe coating, which comprises the following steps:
step (1): weighing 6.0kg of isocyanate, 1.5kg of polyester polyol with molecular weight of 2000, 0.5kg of carbodiimide (water remover) and 2.0kg of propylene carbonate (diluent), adding into a reaction kettle, uniformly stirring, reacting for 6 hours at 120 ℃, removing bubbles (-0.095MPa) in vacuum, and cooling to obtain a component A with NCO content of 12.4%;
step (2): weighing 8.5kg of polyester polyol, 0.5kg of 1, 4' -butanediol (chain extender), 0.1kg of dibutyltin dilaurate (catalyst) and 0.9kg of dehydrated aluminum potassium sulfate dodecahydrate glycerol solution, adding the materials into a reaction kettle, uniformly stirring, vacuumizing (-0.095MPa) for 2.5 hours to remove bubbles, and obtaining a component B;
and (3): adding 8kg of the component A into 10kg of the component B, uniformly mixing, and removing bubbles in vacuum for 30s to obtain the polyurethane coating.
Wherein, in the step (1), the isocyanate is a mixture consisting of 45 percent of 2,4-MDI isomer and 55 percent of 4,4-MDI isomer; in the step (2), the content of dehydrated potassium aluminum sulfate dodecahydrate in the glycerol solution of dehydrated potassium aluminum sulfate dodecahydrate is 5%.
The polyurethane coating prepared in this example was poured onto a flat plate and cured at room temperature to give a clear, bubble-free article.
Comparative example 1
This comparative example prepared a polyurethane coating using the following method:
step (1): weighing 6kg of isocyanate, 2.5kg of polyester polyol with molecular weight of 2000, 0.1kg of carbodiimide (water remover) and 1.4kg of propylene carbonate (diluent), adding into a reaction kettle, uniformly stirring, reacting for 7 hours at 100 ℃, removing bubbles (-0.095MPa) in vacuum, and cooling to obtain a component A with NCO content of 10.4%;
step (2): weighing 7.5kg of polyester polyol, 2.3kg of 1, 4' -butanediol (chain extender) and 0.2kg of dibutyltin dilaurate (catalyst), adding into a reaction kettle, uniformly stirring, and vacuumizing (-0.095MPa) for 3 hours to remove bubbles to obtain a component B;
and (3): adding 8kg of the component A into 10kg of the component B, uniformly mixing, and removing bubbles in vacuum for 30s to obtain the polyurethane coating (shown in figure 2).
Wherein, in the step (1), the isocyanate is a mixture consisting of 40% of 2,4-MDI isomer and 60% of 4,4-MDI isomer.
The polyurethane coating obtained in this example was cast on a flat plate and cured at room temperature to give a transparent article containing a large amount of bubbles.
Comparative example 2
This comparative example prepared a polyurethane coating using the following method:
step (1): weighing 6kg of isocyanate, 2.5kg of polyester polyol with molecular weight of 2000, 0.1kg of carbodiimide (water remover) and 1.4kg of propylene carbonate (diluent), adding into a reaction kettle, uniformly stirring, reacting for 7 hours at 100 ℃, removing bubbles (-0.095MPa) in vacuum, and cooling to obtain a component A with NCO content of 10.4%;
step (2): weighing 7kg of polyester polyol, 2kg of 1, 4' -butanediol (chain extender), 0.2kg of dibutyltin dilaurate (catalyst) and 0.8kg of dehydrated potassium aluminum sulfate dodecahydrate glycerol solution, adding the materials into a reaction kettle in proportion, uniformly stirring, and vacuumizing (-0.095MPa) for 3 hours to remove bubbles to obtain a component B;
and (3): adding 8kg of the component A into 10kg of the component B, uniformly mixing, and removing bubbles in vacuum for 30s to obtain the polyurethane coating (shown in figure 3).
Wherein, in the step (1), the isocyanate is 4,4-MDI isomer; in the step (2), the content of dehydrated aluminum potassium sulfate dodecahydrate in the glycerol solution of dehydrated aluminum potassium sulfate dodecahydrate is 15%.
The polyurethane coating prepared in this example was cast on a flat plate and cured at room temperature to give a whitish opaque article.
As can be seen from comparative example 1, the addition of a proper amount of glycerol solution of dehydrated aluminum potassium sulfate dodecahydrate in the preparation process of component B can eliminate bubbles in the polyurethane coating, because dehydrated aluminum potassium sulfate dodecahydrate and glycerol both have strong water absorbability, and can effectively prevent the generation of chemical bubbles caused by excessive water in the polyol component; dehydrated potassium aluminum sulfate dodecahydrate has strong astringency, and tests prove that the dehydrated potassium aluminum sulfate dodecahydrate is a natural defoaming agent when applied to a polyurethane solvent-free coating system; the glycerol is a natural lubricant, and can remarkably reduce the friction coefficient of a material interface during high-speed stirring in the operation process, thereby playing the role of effectively inhibiting bubbles; in addition, the glycerol (glycerin) is a low molecular alcohol with three functionality degrees, plays a role in optimal heat-sensitive reaction balance in the later stage of thermal reaction in a system, accelerates the curing of the surface of the coating while increasing the internal gel speed, and can effectively improve the working efficiency.
As shown in comparison 2, when 4,4-MDI isomer is selected as the isocyanate, the solution becomes turbid due to the excessively fast reaction, and the mixture of 2,4-MDI isomer and 4,4-MDI isomer can effectively balance the reaction speed and obtain the transparent polyurethane coating.
The polyurethane coating obtained by the invention can be coated on the surfaces of soles and partial vamps of shoes by conventional construction means to form a layer of coating which is transparent as a whole, bright in surface, wear-resistant and waterproof, not only is waterproof and wear-resistant, but also is attractive and fashionable, and simultaneously has no influence on the air permeability of other parts of the vamps. Conventional construction means such as spraying, curtain coating, dipping, brushing, knife coating and the like, and the preferred process is curtain coating and dipping.
Having thus described the invention in detail, it will be apparent to those skilled in the art that modifications and variations are possible in light of the above teachings, and it is intended to cover all such modifications and variations as fall within the true scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a polyurethane coating for shoe coating is characterized by comprising the following steps:
step (1): adding isocyanate, polyester polyol, a water removing agent and a diluent into a reaction kettle in proportion, uniformly stirring, reacting for 6-8 hours at the temperature of 80-120 ℃, removing bubbles in vacuum, and cooling to obtain a component A;
step (2): adding polyester polyol, a chain extender, a catalyst and a glycerol solution of dehydrated aluminum potassium sulfate dodecahydrate into a reaction kettle in proportion, uniformly stirring, vacuumizing for 2-3 hours, and removing bubbles to obtain a component B;
and (3): uniformly mixing the component A and the component B according to the proportion, removing bubbles for 30s in vacuum to obtain the polyurethane coating,
the isocyanate in the step (1) is a mixture of 2,4-MDI isomer and 4,4-MDI isomer.
2. The method of claim 1, wherein the polyurethane coating is prepared by the following steps,
in the step (1), the proportion of isocyanate, polyester polyol, water remover and diluent is as follows: 60-70% of isocyanate, 15-25% of polyester polyol, 1-5% of water removing agent and 5-20% of diluent;
in the step (2), the polyester polyol, the chain extender, the catalyst and the glycerol solution of dehydrated aluminum potassium sulfate dodecahydrate are as follows: 70-85% of polyester polyol, 5-20% of chain extender, 1-3% of catalyst and 8-12% of glycerol solution of dehydrated aluminum potassium sulfate dodecahydrate.
3. The method for preparing the polyurethane paint for the shoe coating according to claim 1, wherein the water scavenger in the step (1) is a carbodiimide-based water scavenger.
4. The method of preparing a polyurethane paint for shoe coating according to claim 1, wherein the diluent in the step (1) is propylene carbonate.
5. The method of preparing a polyurethane coating for a shoe coating according to claim 1, wherein the chain extender in step (2) is 1, 4' -butanediol.
6. The method of preparing a polyurethane coating for a shoe coating according to claim 1, wherein the catalyst in step (2) is dibutyltin dilaurate.
7. The method of claim 1, wherein the content of dehydrated aluminum potassium sulfate dodecahydrate in the glycerol solution of dehydrated aluminum potassium sulfate dodecahydrate is 5-20%.
8. The polyurethane coating produced by the production method according to any one of claims 1 to 7.
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| CN110218512A (en) * | 2019-07-09 | 2019-09-10 | 佛山市南海创意鞋材有限公司 | A kind of bloom mirror surface paint and its preparation method and application |
| CN110484120B (en) * | 2019-08-26 | 2021-06-11 | 东莞市兴茂橡塑科技有限公司 | Bi-component glaze layer material and preparation method and application thereof |
| CN113754855A (en) * | 2021-08-19 | 2021-12-07 | 山东一诺威聚氨酯股份有限公司 | Spray-coating type polyurethane elastomer composition and preparation method thereof |
| CN114479628B (en) * | 2021-12-24 | 2023-03-17 | 佛山市南海起弘新材料科技有限公司 | Polyurethane coating for shoes and preparation method of coating thereof |
| CN115710368B (en) * | 2022-09-20 | 2023-09-19 | 茂泰(福建)新材料科技有限公司 | Surface spraying GPU protective layer, light wear-resisting foaming sole |
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