阅读说明：本技术 一种白刚玉水性聚氨酯涂料及其制备和应用 (White corundum waterborne polyurethane coating and preparation and application thereof ) 是由 方华玉 林鹏 姜兴盛 托马斯·沃尔特施密特 汪忠义 张俊峰 陈剑武 庞南·萨蒂安娜森 于 2019-10-09 设计创作，主要内容包括：本发明涉及化学涂料技术领域,特别涉及一种白刚玉水性聚氨酯涂料及其制备和应用。本发明提供的白刚玉水性聚氨酯涂料,以白刚玉水性聚氨酯涂料重量为基准,包括水性聚氨酯60％-70％,白刚玉浆料15％-35％以及助剂5％-15％；其中,所述白刚玉浆料包含白刚玉35wt％-45wt％、水5wt％-10wt％和分散剂50wt％-60wt％,优选地,包含白刚玉40wt％、水8wt％和分散剂52wt％。本发明提供的白刚玉水性聚氨酯涂料可以用作鞋类、配件或服装上的聚酯或尼龙网的涂层材料,带有这种涂层材料的聚酯或尼龙网制成的鞋类、配件或服装具有极高的耐磨性和耐刮伤性,柔软且耐用,可带来最大的舒适度。(The invention relates to the technical field of chemical coatings, and particularly relates to a white corundum waterborne polyurethane coating as well as preparation and application thereof. The white corundum waterborne polyurethane coating provided by the invention takes the weight of the white corundum waterborne polyurethane coating as a reference, and comprises 60-70% of waterborne polyurethane, 15-35% of white corundum slurry and 5-15% of an auxiliary agent; wherein the white corundum slurry comprises 35-45 wt% of white corundum, 5-10 wt% of water and 50-60 wt% of dispersant, preferably comprises 40 wt% of white corundum, 8 wt% of water and 52 wt% of dispersant. The white corundum waterborne polyurethane coating provided by the invention can be used as a coating material of polyester or nylon net on shoes, accessories or clothes, and the shoes, accessories or clothes made of the polyester or nylon net with the coating material have extremely high wear resistance and scratch resistance, are soft and durable, and can bring the maximum comfort level.)

1. The white corundum aqueous polyurethane coating is characterized by comprising the following components in percentage by weight based on the weight of the white corundum aqueous polyurethane coating:

60-70% of waterborne polyurethane, 15-35% of white corundum slurry and 5-15% of auxiliary agent, wherein the white corundum slurry comprises 35-45 wt% of white corundum, 5-10 wt% of water and 50-60 wt% of dispersing agent, and preferably comprises 40 wt% of white corundum, 8 wt% of water and 52 wt% of dispersing agent.

2. The white corundum aqueous polyurethane coating according to claim 1, wherein the aqueous polyurethane is an aliphatic polyurethane dispersion, the aliphatic polyurethane dispersion has a solid content of 50-60%, an elongation at break of 500% or more, and a pH value of 7-9.

3. The white corundum aqueous polyurethane paint according to claim 1, characterized in that the auxiliaries comprise EFKA4310, acrylic thickeners, aqueous defoamers and amine pH regulators.

4. The preparation method of the white corundum waterborne polyurethane coating is characterized by comprising the following steps:

carrying out primary grinding on white corundum, water and a dispersing agent to obtain white corundum slurry, wherein the white corundum slurry contains 35-45 wt% of white corundum, 5-10 wt% of water and 50-60 wt% of dispersing agent by taking the weight of the white corundum slurry as a reference;

mixing 60-70% of the waterborne polyurethane, 15-25% of the white corundum slurry and 10-20% of the auxiliary agent according to weight percentage, and performing dispersion treatment to obtain uniformly dispersed slurry; and

and post-grinding the slurry to obtain the white corundum waterborne polyurethane coating.

5. The method according to claim 4, wherein the dispersant is EFKA4310, and the white corundum, the water and the dispersant are preliminarily ground at a weight ratio of 40%, 8% and 52%.

6. The preparation method according to claim 4, wherein the aqueous polyurethane is an aliphatic polyurethane dispersion, the aliphatic polyurethane dispersion has a solid content of 50-60%, an elongation at break of 500% or more, and a pH value of 7-9, and the auxiliary agent comprises EFKA4310, an acrylic thickener, an aqueous defoaming agent, and an amine pH regulator.

7. A process for printing the white corundum waterborne polyurethane coating of claim 1, which comprises the following steps:

and (3) curing: adding a curing agent into the white corundum waterborne polyurethane coating, and uniformly stirring, wherein the curing agent is an aliphatic isocyanate polymer;

printing on a whole surface: printing the white corundum waterborne polyurethane coating on the mesh cloth by using a whole face plate, drying for the first time to obtain a first mesh cloth, and cleaning the whole face plate;

screen printing: printing the white corundum waterborne polyurethane coating on the first mesh by using a screen printing plate, drying for the second time to obtain a second mesh, and cleaning the screen printing plate;

and (3) repeated printing: and repeating the steps of full-face printing and screen printing in sequence until the second mesh cloth reaches the preset thickness, stopping printing, and drying for the third time to obtain a printing finished product.

8. The printing process of the white corundum aqueous polyurethane paint as claimed in claim 7, wherein the addition amount of the curing agent is 5-10% based on the weight of the white corundum aqueous polyurethane paint.

9. The printing processing technology of the white corundum waterborne polyurethane coating as claimed in claim 7, wherein the temperature of the first drying and the second drying are both 40 ℃ to 70 ℃, the drying rate is 100mm/s to 200mm/s, and the third drying is drying for 8 hours at 40 ℃ to 60 ℃.

10. The printing process of the white corundum waterborne polyurethane coating according to claim 7, wherein the preset thickness is 0.1-1.6 mm.

Technical Field

The invention relates to the technical field of chemical coatings, and particularly relates to a white corundum waterborne polyurethane coating as well as preparation and application thereof.

Background

The sport shoes refer to shoes worn by people during sports, and the broad concept is specifically as follows: training processes for fitness, leisure, recreational and professional competitive sports and shoe types for formal competitive sports. Due to the particularity of athletic sports, the uppers of athletic shoes are inevitably repeatedly bent and scraped against the ground when the wearer is doing strenuous exercise. Tennis is an example where tennis players often drag the upper on a very rough sandy tennis court, repeatedly scraping with abrasive sand, and severe wear can lead to rapid failure of the sensitive textile upper material.

The vamp has various materials and structure types, and the whole piece type textile or terylene vamp has the characteristics of portability, fit feeling, air permeability and the like, can also have the functions of water resistance, siphon resistance, oil resistance and the like, but does not have the performances of wear resistance, scratch resistance and the like, and is limited to the application in the field of competitive sports. Chinese patent CN104452011B discloses a PVC coated yarn for making a sports shoe upper and a production process thereof, the specific structure of the product formed by the process is as follows: an intermediate coating for improving the bonding force is arranged outside the polyester fiber core wire, and a PVC coating layer is arranged outside the intermediate coating. The finished product replaces polyester fabric on sports shoes with PVC coated yarn, so that the wear resistance of vamp fabric is greatly improved, and the finished product has the advantages of good stability, strong anti-fouling capability and the like. However, the vamp made of the material has a three-layer structure, and has questionable light and air permeability, low flexibility and complex production process.

The waterborne polyurethane coating has the characteristics of excellent bonding performance, good chemical resistance, water resistance, solvent resistance, flexible operability and the like, and is widely applied to finishing coatings on the surfaces of articles such as automobiles, furniture and the like, environment-friendly coatings of buildings and houses, and coating layers of clothes and shoes. However, the waterborne polyurethane coating used in the current market is expensive and low in wear resistance, and cannot meet the requirements of sports shoes on high quality, low cost, wear resistance and wear resistance.

Disclosure of Invention

In order to solve the technical problems, the invention provides a white corundum waterborne polyurethane coating with super-strong wear resistance and scratch resistance and good flexibility, and a preparation method, a printing process and application thereof.

In order to achieve the above object, according to a first aspect of the present invention, there is provided a white corundum aqueous polyurethane coating, including: 60-70% of waterborne polyurethane, 15-35% of white corundum slurry and 5-15% of auxiliary agent, wherein the white corundum slurry comprises 35-45 wt% of white corundum, 5-10 wt% of water and 50-60 wt% of dispersing agent. The white corundum slurry comprises 35-45 wt% of white corundum, 5-10 wt% of water and 50-60 wt% of dispersing agent, but the inventor finds that the white corundum slurry obtained by grinding the white corundum, the water and the dispersing agent according to a specific proportion can play the best role in enhancing the performance of the white corundum waterborne polyurethane coating. Preferably, the white corundum paint contains 40 wt% of white corundum, 8 wt% of water and 52 wt% of dispersing agent. Preferably, the dispersant is EFKA4310 (EFKA-4310 dispersant).

In some exemplary embodiments of the invention, the aqueous polyurethane is an aliphatic polyurethane dispersion having a solids content of 50% to 60%, an elongation at break of greater than or equal to 500%, and a pH of 7 to 9.

In a more preferred embodiment of the present invention, the auxiliary agent comprises EFKA4310, an acrylic thickener, an aqueous defoaming agent, and an amine pH adjuster. EFKA4310 is an Effka (EFKA-4310) dispersant, which is a polymer dispersant polymerized by using a controlled free radical technology (CFRP) and suitable for solvent-based industrial coatings and automobile coatings. EFKA4310 has high pigment dispersing performance and wide compatibility with various resin systems.

Different from the prior art, the technical scheme adds the corundum powder into the waterborne polyurethane in a slurry fluid form to form the liquid coating. The white corundum particles in the white corundum waterborne polyurethane coating provided by the invention form a uniformly dispersed state in waterborne polyurethane, and a compact 3D cubic positioned crystal structure is presented, so that the white corundum waterborne polyurethane coating has extremely high hardness and flexibility.

The second aspect of the invention provides a preparation method of a white corundum waterborne polyurethane coating, which comprises the following steps: carrying out primary grinding on white corundum, water and a dispersing agent to obtain white corundum slurry, wherein the white corundum slurry contains 35-45 wt% of white corundum, 5-10 wt% of water and 50-60 wt% of dispersing agent by taking the weight of the white corundum slurry as a reference;

mixing 60-70% of the waterborne polyurethane, 15-25% of the white corundum slurry and 10-20% of the auxiliary agent according to weight percentage, and performing dispersion treatment to obtain uniformly dispersed slurry; and

and post-grinding the slurry to obtain the white corundum waterborne polyurethane coating.

The white corundum slurry comprises 35-45 wt% of white corundum, 5-10 wt% of water and 50-60 wt% of a dispersing agent, but the inventor finds that the viscosity of the white corundum slurry is reduced and the wear resistance is further reduced if the adding amount of the dispersing agent is too high, so that the white corundum slurry obtained by grinding the white corundum slurry, the water and the dispersing agent in a specific ratio can play the best role in enhancing the performance of the white corundum waterborne polyurethane coating.

In a more preferred embodiment of the present invention, the dispersant is EFKA4310 (EFKA-4310 dispersant), and the white corundum, the water and the dispersant are primarily ground at a weight ratio of 40%, 8% and 52%.

In a more preferred embodiment of the present invention, the aqueous polyurethane is an aliphatic polyurethane dispersion, the aliphatic polyurethane dispersion has a solid content of 50% to 60%, an elongation at break of 500% or more, and a pH of 7 to 9, and the auxiliary agent includes EFKA4310 (EFKA-4310 dispersant), an acrylic thickener, an aqueous defoaming agent, and an amine pH adjuster.

Different from the prior art, the white corundum waterborne polyurethane coating prepared by the technical scheme has the advantages that the process is simple, raw materials are easy to obtain, white corundum is prepared and ground into slurry, the slurry is added into the waterborne polyurethane coating according to a certain proportion, so that the white corundum waterborne polyurethane coating with excellent wear resistance and scratch resistance is obtained, and used instruments and equipment are common and are suitable for production and application.

In a third aspect of the present invention, there is provided a printing process of the white corundum aqueous polyurethane coating according to the first aspect of the present invention, comprising the following steps:

and (3) curing: adding a curing agent into the white corundum waterborne polyurethane coating, and uniformly stirring, wherein the curing agent is an aliphatic isocyanate polymer;

printing on a whole surface: printing the white corundum waterborne polyurethane coating on the mesh cloth by using a whole face plate, drying for the first time to obtain a first mesh cloth, and cleaning the whole face plate;

screen printing: printing the white corundum waterborne polyurethane coating on the first mesh by using a screen printing plate, drying for the second time to obtain a second mesh, and cleaning the screen printing plate;

and (3) repeated printing: and repeating the steps of full-face printing and screen printing in sequence until the second mesh cloth reaches the preset thickness, stopping printing, and drying for the third time to obtain a printing finished product.

In a more preferred embodiment of the present invention, the curing agent is added in an amount of 5% to 10% based on the weight of the white corundum aqueous polyurethane coating.

As a more preferable scheme of the invention, the temperature of the first drying and the second drying is 40-70 ℃, the drying speed is 100-200 mm/s, and the third drying is drying for 8h at 40-60 ℃.

In a more preferred embodiment of the present invention, the predetermined thickness is 0.1 to 1.6 mm.

The white corundum waterborne polyurethane coating provided by the invention can be used as a coating material on substrates such as polyester or nylon nets on shoes, accessories or clothes.

Different from the prior art, the technical scheme adopts a special printing process to print the white corundum waterborne polyurethane coating on the mesh fabric base material, so that the wear resistance of a printed finished product (the mesh fabric with the coating) is enhanced, and the bending resistance of the coating is less influenced.

Drawings

Fig. 1 is a schematic view of a composition structure of a white corundum aqueous polyurethane coating according to a specific embodiment.

Description of reference numerals:

101. aqueous polyurethane;

102. white corundum;

103. and (4) screen cloth.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments.

In the embodiment of the invention, the waterborne polyurethane is a novel polyurethane system which takes water as a dispersion medium instead of an organic solvent, and is also called water-dispersed polyurethane, water-based polyurethane or water-based polyurethane; according to the particle size and appearance, the polyurethane emulsion can be divided into polyurethane aqueous solution (the particle size is less than 0.001 micrometer, the appearance is transparent), polyurethane aqueous dispersion (the particle size is 0.001-0.1 micrometer, the appearance is semitransparent) and polyurethane emulsion (the particle size is more than 0.1 micrometer, the appearance is white and turbid); aqueous polyurethanes can be classified as anionic, cationic, and nonionic depending on whether the side chain or main chain of the polyurethane molecule contains an ionic group, i.e., is an ionomer (ionomer). The aqueous polyurethane containing anions and cations is also called ionomer type aqueous polyurethane.

In the embodiment of the invention, the polyurethane aqueous dispersion (with the particle diameter of 0.001-0.1 micron and semitransparent appearance) is prepared by adopting a substance with salifying hydrophilic groups to react with-NCO groups of a prepolymer to generate hydrophilic polyurethane salt, and the polyurethane salt can be directly dispersed in water by stirring without adding an emulsifier to obtain the semitransparent dispersion. During the film forming process, water is gradually removed, the molecular chains and the ionic groups are regularly arranged, so that not only is electrostatic action and hydrogen bonding force exist, but also cross-linking reaction occurs among molecules to form a network structure. Because of the absence of the emulsifier, the particles are not sensitive to mechanical stirring, heating or dilution and are electrolyte-resistant; the adhesive film is firm and elastic, and has strong adhesive force. The aliphatic polyurethane dispersion has a solid content of 50-60%, an elongation at break of 500% or more, and a pH value of 7-9.

The dispersant used in the specific examples of the present invention was 4310 by EFKA, Inc.

The adjuvant acrylic thickener used in the specific embodiment of the present invention is a synthetic thickener PTF from Alcoprint, Inc. abroad, the Chinese name is "Ake seal PTF". Is a white dispersion and belongs to an anionic type. It can be used in full-aqueous phase and semi-emulsion system, and can be thickened when meeting acid and alkali. The main component of PTF is polyacrylic acid, and the average relative molecular mass of PTF is controlled by adding a cross-linking agent, so that the long-chain connection is not too long, and the high average relative molecular mass can be ensured.

The water-based antifoaming agent used in the specific embodiment of the present invention is Nantong Deyi New materials company 8009, and the alcamines pH value regulator is modified triethanolamine.

The curing agent used in the specific embodiment of the present invention is Basonat waterborne isocyanate curing agent Basonat HW 100.

In the specific embodiment of the invention, the primary grinding and the post-grinding are both performed by using a sand mill, which is purchased from FWE horizontal sand mill of Shanghai Fulai company.