阅读说明：本技术 一种耐污自修复涂料及其制备方法 (Stain-resistant self-repairing coating and preparation method thereof ) 是由 李曼 毛耀全 梁明 于 2021-07-26 设计创作，主要内容包括：本发明公开了一种耐污自修复涂料及其制备方法,属于自修复涂料技术领域。它包括聚氨酯树脂、改性丙烯酸树脂、固化剂、有机溶剂,且所述改性丙烯酸树脂的质量是聚氨酯树脂质量的1～2倍,有机溶剂的质量是两种树脂总质量的2～3倍,固化剂质量是两种树脂总质量的1～1.5倍。本发明在涂料体系中搭配苯乙烯改性丙烯酸树脂,固化成膜后得到具有亲油效果的热固性热修涂料,具有高光泽、热修复效果佳,良好的抗记号笔效果,良好的抗化油器效果,没有雨斑、黄变等不良现象。(The invention discloses a stain-resistant self-repairing coating and a preparation method thereof, belonging to the technical field of self-repairing coatings. The modified acrylic resin is 1-2 times of the mass of the polyurethane resin, the mass of the organic solvent is 2-3 times of the total mass of the two resins, and the mass of the curing agent is 1-1.5 times of the total mass of the two resins. According to the invention, the styrene modified acrylic resin is matched in the coating system, and the thermosetting hot repair coating with the oleophylic effect is obtained after curing and film forming, so that the coating has the advantages of high gloss, good hot repair effect, good marker pen resistance effect, good carburetor resistance effect, no raindrop, no yellowing and other adverse phenomena.)

1. A stain-resistant self-repairing coating is characterized in that: the modified acrylic resin is 1-2 times of the polyurethane resin in mass, the organic solvent is 2-3 times of the total mass of the two resins in mass, and the curing agent is 1-1.5 times of the total mass of the two resins in mass;

the modified acrylic resin is one of amino modified acrylic thermosetting resin, styrene modified acrylic thermosetting resin and polyurethane modified acrylic thermosetting resin.

2. The stain-resistant self-repairing coating of claim 1, wherein: the organic solvent is one or a combination of more of N, N dimethylformamide, ethyl acetate, butyl acetate, acetone, cyclohexanone and xylene.

3. The stain-resistant self-repairing coating according to claim 3, wherein: the organic solvent is a composite solvent of butyl acetate, xylene and cyclohexanone in a mass ratio of 3:2: 1.

4. The stain-resistant self-repairing coating of claim 1, wherein: the curing agent is one or two of TDI curing agent, MDI curing agent, HDI curing agent and XDI curing agent.

5. The preparation method of the stain-resistant self-repairing coating according to any one of claims 1 to 4, which is characterized by mainly comprising the following steps:

s1, preparing a heat-curing coating: mixing polyurethane resin, modified acrylic resin, an organic solvent and a flatting agent according to a certain proportion, fully stirring until the two resins are completely dissolved, and the whole system becomes a colorless transparent solution with a certain viscosity, and then sealing and storing the solution and matching with a curing agent for use;

s2, thermal curing: and mixing the prepared thermosetting coating and a curing agent, uniformly stirring the mixture fully, uniformly coating the mixture on a basic transparent film by using a coating rod, then placing the film in an environment of 110-130 ℃ for thermal drying for 120-180 s, and obtaining the lipophilic stain-resistant self-repairing film after the thermal drying.

6. The method for preparing the stain-resistant self-repairing coating according to claim 5, wherein in S2, the coating rod is a wire rod with any specification within the range of 10-100 μm, and the basic transparent film is one of common TPU film, TPH film and PVC film.

Technical Field

The invention relates to a stain-resistant self-repairing coating and a preparation method thereof, belonging to the technical field of self-repairing coatings.

Background

The self-repairing coating is a name which is proposed in the 90 s of the 20 th century and can be called as an intelligent coating, and usually refers to an organic polyurethane compound coating which has a self-repairing function after a coating is damaged or has a self-repairing function under a certain condition. The scratch gap is automatically repaired by means of the flowing of the coating and the mechanical deformation of an object and forming a chemical bond or a physical action, so that the scratch gap becomes an intrinsic repair type. Thus, the self-healing coating does not require the addition of a specific healing agent, nor is it limited to a particular type of damage. The research on the aspect is very active, the chemical problem needs to be deepened, in order to meet different environmental tests, different formulas of the self-repairing coating have been developed, and different surface characteristics are highlighted specifically, such as excellent self-repairing performance, or excellent stain resistance, smoothness, high light performance and the like.

The self-repairing coating is prepared by utilizing the concept of delaying elasticity of a high polymer in high polymer physics. The principle is that when the temperature is higher than the glass transition temperature of the resin (or a certain component in the resin) or higher than the viscous flow temperature, the resin flows, and the necessary coating film property is obtained when the temperature is reduced. Such coatings have been successful in commercial applications for small area damage. Such coatings are commonly referred to in the coatings industry as thermal repair coatings. In addition, the self-repairing coating also has super-strong corrosion resistance and aging resistance. In the face of the feedback requirement of the current market, most of the coatings on the market are oleophobic self-repairing coatings, and the oleophylic self-repairing coatings are rarely involved, so that the development and application of the oleophylic self-repairing coatings are a topic with broad prospects.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the oleophylic stain-resistant self-repairing coating and the preparation method thereof are provided to solve the oleophobic characteristic of common stain-resistant self-repairing coatings, and the oleophylic problem of the stain-resistant self-repairing coating is realized through the participation of modified oleophylic acrylic resin, and the oleophylic problem of the stain-resistant self-repairing coating is realized by adopting the following technical scheme:

the stain-resistant self-repairing coating comprises polyurethane resin, modified acrylic resin, a curing agent and an organic solvent, wherein the mass of the modified acrylic resin is 1-2 times that of the polyurethane resin, the mass of the organic solvent is 2-3 times that of the total mass of the two resins, and the mass of the curing agent is 1-1.5 times that of the total mass of the two resins.

As a preferable example, the modified acrylic resin is one of amino-modified acrylic thermosetting resin, styrene-modified acrylic thermosetting resin, and urethane-modified acrylic thermosetting resin.

Further, the modified acrylic resin is a styrene-modified acrylic thermosetting resin.

As a preferable example, the organic solvent is one or a combination of more of N, N dimethylformamide, ethyl acetate, butyl acetate, acetone, cyclohexanone and xylene.

As a preferred example, the organic solvent is a composite solvent of butyl acetate, xylene and cyclohexanone in a mass ratio of 3:2: 1.

As a preferred example, the curing agent is one or two of TDI curing agent, MDI curing agent, HDI, XDI curing agent.

Further, the curing agent is one of an HDI curing agent and an XDI curing agent.

A preparation method of a stain-resistant self-repairing coating mainly comprises the following steps:

s1, preparing a heat-curing coating: mixing polyurethane resin, modified acrylic resin, an organic solvent and a flatting agent according to a certain proportion, fully stirring until the two resins are completely dissolved, and the whole system becomes a colorless transparent solution with a certain viscosity, and then sealing and storing the solution and matching with a curing agent for use;

s2, thermal curing: and mixing the prepared thermosetting coating and a curing agent, uniformly stirring the mixture fully, uniformly coating the mixture on a basic transparent film by using a coating rod, then placing the film in an environment of 110-130 ℃ for thermal drying for 120-180 s, and obtaining the lipophilic stain-resistant self-repairing film after the thermal drying.

As a preferable example, in S2, the coating rod has a wire rod with any one specification of 10-100 μm, and the base transparent film is one of common TPU film, TPH film and PVC film.

Furthermore, the specification of the coating rod is 20 μm, and the transparent film is a common TPU film; the drying temperature is 120 ℃, and the drying time is 120 s.

The invention has the beneficial effects that: according to the invention, the styrene modified acrylic resin is matched in the coating system, and the thermosetting hot repair coating with the oleophylic effect is obtained after curing and film forming, so that the coating has the advantages of high gloss, good hot repair effect, good marker pen resistance effect, good carburetor resistance effect, no raindrop, no yellowing and other adverse phenomena.

Drawings

FIG. 1 is a graph of the contamination resistance test of the present invention during writing with a marker;

FIG. 2 is a stain resistance test chart of the present invention after alcohol wiping;

FIG. 3 is a graph of a thermal repair test of the present invention before scratch repair;

fig. 4 is a thermal repair test chart after scratch repair according to the present invention.

Detailed Description

In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further explained by combining the specific drawings and the embodiments.

Example 1

The preparation method of the self-repairing coating comprises the following steps:

s1, preparing a heat-curing coating: mixing 10g of polyurethane resin, 10g of modified acrylic resin, 20g of butyl acetate, 20g of xylene, 20g of cyclohexanone and 1% of flatting agent, fully stirring until the resin is completely dissolved, and the whole system becomes a colorless transparent solution with certain viscosity, and then sealing and storing;

s2, thermal curing: mixing 8g of the prepared thermosetting coating and 2g of HDI curing agent, fully and uniformly stirring, uniformly coating on a basic TPU film by a coating rod with the thickness of 50 mu m, then putting the TPU film in an environment with the temperature of 110 ℃ for heat drying for 180s, and obtaining the stain-resistant self-repairing coating film with oleophylic effect after heat drying.

Example 2

The preparation method of the self-repairing coating comprises the following steps:

s1, preparing a heat-curing coating: mixing 10g of polyurethane resin, 20g of modified acrylic resin, 25g of butyl acetate, 25g of xylene, 25g of cyclohexanone and 1% of flatting agent, fully stirring until the resin is completely dissolved, and the whole system becomes a colorless transparent solution with certain viscosity, and then sealing and storing;

s2, thermal curing: mixing 8g of the prepared thermosetting coating and 2g of HDI curing agent, fully and uniformly stirring, uniformly coating on a basic TPU film by a coating rod with the thickness of 50 mu m, then putting the TPU film in an environment with the temperature of 110 ℃ for heat drying for 180s, and obtaining the stain-resistant self-repairing coating film with oleophylic effect after heat drying.

Example 3

The preparation method of the self-repairing coating comprises the following steps:

s1, preparing a heat-curing coating: mixing 10g of polyurethane resin, 10g of modified acrylic resin, 20g of butyl acetate, 20g of xylene, 20g of cyclohexanone and 1% of flatting agent, fully stirring until the resin is completely dissolved, and the whole system becomes a colorless transparent solution with certain viscosity, and then sealing and storing;

s2, thermal curing: mixing 8g of the prepared thermosetting coating and 2g of XDI curing agent, fully and uniformly stirring, uniformly coating on a basic TPU film by a coating rod with the thickness of 50 mu m, then putting the TPU film into an environment with the temperature of 110 ℃ for heat drying for 180s, and obtaining the stain-resistant self-repairing coating film with oleophylic effect after heat drying.

Example 4

The preparation method of the self-repairing coating comprises the following steps:

s1, preparing a heat-curing coating: mixing 10g of polyurethane resin, 20g of modified acrylic resin, 25g of butyl acetate, 25g of xylene, 25g of cyclohexanone and 1% of flatting agent, fully stirring until the resin is completely dissolved, and the whole system becomes a colorless transparent solution with certain viscosity, and then sealing and storing;

s2, thermal curing: mixing 8g of the prepared thermosetting coating and 2g of HDI curing agent, fully and uniformly stirring, uniformly coating on a basic TPU film by a coating rod with the thickness of 50 mu m, then putting the TPU film in an environment with the temperature of 110 ℃ for heat drying for 180s, and obtaining the stain-resistant self-repairing coating film with oleophylic effect after heat drying.

Example 5

The preparation method of the self-repairing coating comprises the following steps:

s1, preparing a heat-curing coating: mixing 10g of polyurethane resin, 10g of modified acrylic resin, 20g of butyl acetate, 20g of xylene, 20g of cyclohexanone and 1% of flatting agent, fully stirring until the resin is completely dissolved, and the whole system becomes a colorless transparent solution with certain viscosity, and then sealing and storing;

s2, thermal curing: and mixing 8g of the prepared thermosetting coating and 2g of HDI curing agent, fully and uniformly stirring, uniformly coating on a basic TPU film by using a 20-micron coating rod, then putting the TPU film into an environment at 110 ℃ for thermal drying for 120s, and obtaining the stain-resistant self-repairing coating film with oleophylic effect after the thermal drying.

Example 6

The preparation method of the self-repairing coating comprises the following steps:

s1, preparing a heat-curing coating: mixing 10g of polyurethane resin, 10g of modified acrylic resin, 20g of butyl acetate, 20g of xylene, 20g of cyclohexanone and 1% of flatting agent, fully stirring until the resin is completely dissolved, and the whole system becomes a colorless transparent solution with certain viscosity, and then sealing and storing;

s2, thermal curing: mixing 8g of the prepared thermosetting coating and 2g of XDI curing agent, fully and uniformly stirring, uniformly coating on a basic TPU film by a coating rod with the diameter of 20 mu m, then putting the TPU film into an environment with the temperature of 110 ℃ for thermal drying for 120s, and obtaining the stain-resistant self-repairing coating film with oleophylic effect after thermal drying.

Example 7

The preparation method of the self-repairing coating comprises the following steps:

s1, preparing a heat-curing coating: mixing 10g of polyurethane resin, 10g of modified acrylic resin, 30g of butyl acetate, 20g of xylene, 10g of cyclohexanone and 1% of flatting agent, fully stirring until the resin is completely dissolved, and the whole system becomes a colorless transparent solution with certain viscosity, and then sealing and storing;

s2, thermal curing: mixing 8g of the prepared thermosetting coating and 2g of HDI curing agent, fully and uniformly stirring, uniformly coating on a basic TPU film by a 20-micron coating rod, then placing the TPU film in an environment of 120 ℃ for thermal drying for 120s, and obtaining the stain-resistant self-repairing coating film with oleophylic effect after thermal drying.

Example 8

The preparation method of the self-repairing coating comprises the following steps:

s1, preparing a heat-curing coating: mixing 10g of polyurethane resin, 10g of modified acrylic resin, 30g of butyl acetate, 10g of xylene, 20g of cyclohexanone and 1% of flatting agent, fully stirring until the resin is completely dissolved, and the whole system becomes a colorless transparent solution with certain viscosity, and then sealing and storing;

s2, thermal curing: mixing 8g of the prepared thermosetting coating and 2g of HDI curing agent, fully and uniformly stirring, uniformly coating on a basic TPU film by a 20-micron coating rod, then placing the TPU film in an environment of 120 ℃ for thermal drying for 120s, and obtaining the stain-resistant self-repairing coating film with oleophylic effect after thermal drying.

Example 9

The preparation method of the self-repairing coating comprises the following steps:

s1, preparing a heat-curing coating: mixing 10g of polyurethane resin, 15g of modified acrylic resin, 30g of butyl acetate, 20g of xylene, 10g of cyclohexanone and 1% of flatting agent, fully stirring until the resin is completely dissolved, and the whole system becomes a colorless transparent solution with certain viscosity, and then sealing and storing;

s2, thermal curing: mixing 8g of the prepared thermosetting coating and 2g of HDI curing agent, fully and uniformly stirring, uniformly coating on a basic TPU film by a coating rod with the thickness of 50 mu m, then putting the TPU film in an environment with the temperature of 110 ℃ for heat drying for 180s, and obtaining the stain-resistant self-repairing coating film with oleophylic effect after heat drying.

Example 10

The preparation method of the self-repairing coating comprises the following steps:

s1, preparing a heat-curing coating: mixing 10g of polyurethane resin, 15g of modified acrylic resin, 30g of butyl acetate, 25g of xylene, 20g of cyclohexanone and 1% of flatting agent, fully stirring until the resin is completely dissolved, and the whole system becomes a colorless transparent solution with certain viscosity, and then sealing and storing;

s2, thermal curing: mixing 8g of the prepared thermosetting coating and 2g of HDI curing agent, fully and uniformly stirring, uniformly coating on a basic TPU film by a coating rod with the thickness of 50 mu m, then putting the TPU film in an environment with the temperature of 110 ℃ for heat drying for 180s, and obtaining the stain-resistant self-repairing coating film with oleophylic effect after heat drying.

Example 11

The preparation method of the self-repairing coating comprises the following steps:

s1, preparing a heat-curing coating: mixing 10g of polyurethane resin, 10g of modified acrylic resin, 20g of butyl acetate, 20g of xylene, 20g of cyclohexanone and 1% of flatting agent, fully stirring until the resin is completely dissolved, and the whole system becomes a colorless transparent solution with certain viscosity, and then sealing and storing;

s2, thermal curing: mixing 8g of the prepared thermosetting coating and 2g of HDI curing agent, fully and uniformly stirring, uniformly coating on a basic TPU film by a 20-micron coating rod, then putting the TPU film in an environment of 120 ℃ for heat drying for 180s, and obtaining the stain-resistant self-repairing coating film with oleophylic effect after heat drying.

FIG. 1 shows that the oil pen is coated on the surface of the stain-resistant self-repairing film, and the coating film has good oleophilic property, and FIG. 2 shows that the film of FIG. 1 has good stain-resistant property after being wiped by ethanol; FIG. 3 is a surface of a self-repairing film brushed by a copper brush, FIG. 4 is an effect of the film of FIG. 3 after being rinsed by hot water at 60 ℃ for 10 seconds, scratches can be seen to be repaired, and the coating film is proved to have good self-repairing performance.

The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.