A transparent, wear-resistant and temperature-resistant protective coating for electronic products

Abstract

The present invention discloses a transparent, wear-resistant and temperature-resistant electronic protective coating, which is composed of a prepolymer and a latent siloxane curing agent. The prepolymer is made by mixing perfluoropolyether alcohol, diisocyanate compounds, composite polyetheramine, metal catalysts and organic solvents. The transparent, wear-resistant and temperature-resistant electronic product protective coating of the present invention can be cured and painted at room temperature, with simple operation. The prepared transparent, wear-resistant and temperature-resistant electronic product protective coating has the characteristics of wear resistance, high transparency, stain resistance and liquid blocking, etc.

Description

Technical Field

[0001] The present invention belongs to the technical field of antifouling coatings, and particularly relates to a transparent, wear-resistant and temperature-resistant protective coating for electronic products. Background Art

[0002] As a functional coating, the electronic protective coating has the characteristics of good moisture resistance and anti-oil pollution. It can protect the surface from fingerprints, graffiti, moisture and other pollutants, and make the surface easier to clean. Therefore, it has a wide range of applications in the fields of medical treatment, flexible display, microelectronic coating, flexible electronic main board, etc. The construction methods of electronic protective surfaces can be divided into two types. The first is a superhydrophobic / superoleophobic surface with micro / nanostructures. Usually, the contact angle of a liquid droplet on its surface is greater than 150°, and the sliding angle is less than 10°. However, micro / nanostructures are usually constructed by methods such as etching and electrochemistry. These methods not only rely on specific equipment, but also have complex processes, low production efficiency, poor stability and wear resistance, and poor transparency, etc.

[0003] Another antifouling surface has a smooth surface. The contact angle of the liquid droplet surface is less than 120°, but the liquid droplet will easily slide off when the surface is slightly tilted. Different from the antifouling surface with micro / nanostructures, the smooth antifouling surface has a low surface roughness, so good optical transparency can be achieved. Generally, low surface energy molecules or polymers are covalently grafted onto the molecular chain of the coating matrix or fixed on the substrate surface to form a micro-nano-like liquid monolayer to achieve water and oil repellency. The commonly selected coating matrix is polyurethane or polyurea. Due to its organic composition, the antifouling coating based on polyurethane or polyurea has poor surface hardness. During the production or consumer use of electronic products, due to touching or friction, the waterproof and anti-fouling performance of the coating is likely to decline, unable to meet the actual application requirements.

[0004] Currently, there have been some reports on improving the coating hardness by introducing inorganic nanoparticles. However, the inorganic nanoparticles are difficult to disperse and have a complex structure, and often make the coating opaque. In addition, most of the existing antifouling coatings involve high-temperature thermal curing. This curing method is time-consuming, energy-consuming, and not suitable for heat-sensitive substrates.

[0005] Polyurea is prepared by the addition polymerization reaction of isocyanate and amino group. This polymerization reaction has extremely high activity and can be cured at room temperature. However, due to the too high reaction rate, in order to complete the coating, a two-component spraying form is adopted in industry. This spraying equipment is inconvenient for transportation and operation, and the performance of polyurea cannot be regulated. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art in the background, and provide a transparent, wear-resistant and temperature-resistant protective coating for electronic products.

[0007] Another object of the present invention is to provide a method for preparing a transparent, wear-resistant and temperature-resistant protective coating for electronic products.

[0008] The technical solution of the present invention is as follows:

[0009] A transparent, wear-resistant and temperature-resistant protective coating for electronic products, which is composed of a prepolymer and a latent silicone curing agent.

[0010] The prepolymer is prepared by mixing perfluoropolyether alcohol, diisocyanate compound, composite polyetheramine, metal catalyst and organic solvent.

[0011] The structural formula of the perfluoropolyether alcohol is n = 1 - 10;

[0012] The structural formula of the latent silicone curing agent is R is Its degree of branching is 0.6 - 0.85.

[0013] In a preferred embodiment of the present invention, the prepolymer is prepared by mixing perfluoropolyether alcohol, diisocyanate compound, composite polyetheramine, metal catalyst and organic solvent in a mass ratio of 1.5 - 3:50 - 100:0 - 50:1.5 - 3:100 - 800.

[0014] Further preferably, the preparation method of the prepolymer includes: adding a quantitative amount of perfluoropolyether alcohol, metal catalyst and diisocyanate compound into a clean reaction kettle, slowly dropping the composite polyetheramine while stirring at 0 - 10°C, and controlling the temperature to react at 0 - 10°C for 1 - 3 h and then raising the temperature to 60 - 90°C, and then holding the temperature for reaction for 4 - 8 h to obtain the prepolymer.

[0015] In a preferred embodiment of the present invention, the composite polyetheramine is at least one of D230, D400 and D2000.

[0016] In a preferred embodiment of the present invention, the metal catalyst is at least one of potassium acetate, potassium octoate, potassium oleate, stannous octoate and dibutyltin dilaurate.

[0017] In a preferred embodiment of the present invention, the diisocyanate compound is at least one of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (HMDI).

[0018] In a preferred embodiment of the present invention, the organic solvent is a ketone organic solvent, an ester organic solvent, a fluorine organic solvent or a chlorine organic solvent.

[0019] Further preferably, the ketone organic solvent is at least one of acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; the ester organic solvent is at least one of methyl acetate, ethyl acetate, propyl acetate and butyl acetate; the fluorine organic solvent is at least one of 2-(trifluoromethyl)-3-ethoxydodecafluorohexane (7500), 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-trifluoromethylpentane (7300), 1,1,1,2,2,3,3,4,4,4-nonafluoro-4-ethoxybutane (7200), 1,1,1,2,2,3,3,4,4,4-nonafluoro-4-methoxybutane (7100), 1,1,1,2,3,3-hexafluoro-3-(2,2,2-trifluoroethoxy)propane (HFE449) or 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (HFE458), hexafluoropropylene dimer, hexafluoropropylene trimer, 2H,3H-decafluoropentane, hexadecafluoroheptane and octadecafluorooctane; and the chlorine organic solvent is dichloromethane and / or chloroform.

[0020] In a preferred embodiment of the present invention, the mass ratio of perfluoropolyether alcohol, diisocyanate compound, composite polyetheramine, metal catalyst, organic solvent and latent siloxane curing agent is 1.5-3:50-100:0-50:1.5-3:100-800:10-100.

[0021] The beneficial effects of the present invention are as follows:

[0022] 1. The inorganic component contained in the raw materials of the present invention is siloxane, which has good solubility and can participate in the coating curing reaction, avoiding the problem of sedimentation of traditional inorganic fillers.

[0023] 2. The latent siloxane curing agent in the present invention can form a one-component polyurea coating, which is convenient for painting.

[0024] 3. The latent siloxane curing agent in the present invention can expose amino groups under the action of moisture, realizing the controllable curing of the polyurea coating at room temperature.

[0025] 4. The transparent wear-resistant and temperature-resistant electronic product protective coating prepared by the present invention is an organic-inorganic hybrid coating, which ensures the transparency of the coating while improving the hardness of the coating.

[0026] 5. The main body of the transparent wear-resistant and temperature-resistant electronic product protective coating prepared by the present invention is a polyurea structure, which exhibits the advantages of acid and alkali resistance, organic solvent resistance, aging resistance, etc.

[0027] 6. The fluorine-containing substance in the transparent, wear-resistant and room-temperature curable polyurea antifouling coating prepared by the present invention is monofunctional, enabling the fluorine-containing substance to form a liquid-like monolayer on the coating surface. At a low addition amount, it endows the coating with low surface energy and good antifouling performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is the Fourier infrared spectrum diagram of the transparent, wear-resistant and temperature-resistant electronic product protection coating prepared in Example 1 of the present invention.

[0029] Figure 2 It is the thermogravimetric curve diagram of the transparent, wear-resistant and temperature-resistant electronic product protection coating prepared in Example 1 of the present invention.

[0030] Figure 3 It is the physical diagram of the transparent, wear-resistant and temperature-resistant electronic product protection coating prepared in Example 1 of the present invention.

[0031] Figure 4 It is the visible light transmittance curve diagram of the transparent, wear-resistant and temperature-resistant electronic product protection coating prepared in Example 1 of the present invention.

[0032] Figure 5 It is the anti-graffiti effect diagram of the transparent, wear-resistant and temperature-resistant electronic product protection coating prepared in Example 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] The technical solutions of the present invention will be further described and illustrated below through specific embodiments in conjunction with the drawings.

[0034] The structural formula of the perfluoropolyether alcohol in the following examples is n = 1 - 10; the structural formula of the latent siloxane curing agent is R is

[0035] Example 1

[0036] Isophorone diisocyanate (50 parts by mass), perfluoropolyether alcohol with a molecular weight of 1700 (1.5 parts by mass), and dibutyltin dilaurate (1.5 parts by mass) were respectively added to a clean reaction flask. Then ethyl acetate (850 parts by mass) was added, and the mixture was placed in an oil bath at 70 °C and kept reacting for 5 h. After the reaction ended, a prepolymer was obtained.

[0037] After the above prepolymer was cooled to room temperature, a latent siloxane curing agent (100 parts by mass) with a branching degree of 0.85 and R being was added thereto, and the mixture was stirred to obtain a one-component polyurea coating. The one-component polyurea coating was drop-coated onto a substrate and cured at room temperature for 24 h to obtain a coating as shown in Figures 1 to 5The transparent wear-resistant and temperature-resistant protective coating for electronic products as shown. The specific properties of the transparent wear-resistant and temperature-resistant protective coating for electronic products are shown in Table 1.

[0038] Example 2

[0039] Isophorone diisocyanate (50 parts by mass), perfluoropolyether alcohol with a molecular weight of 1700 (1.5 parts by mass), and dibutyltin dilaurate (1.5 parts by mass) were respectively added into a clean reaction flask. Then ethyl acetate (850 parts by mass) was added, and the mixture was placed in an ice-water bath at 0 °C. Polyetheramine D400 (50 parts by mass) was slowly added dropwise. After the addition was completed, the mixture was reacted at room temperature for 5 h, then heated to 70 °C and kept at this temperature for 5 h. After the reaction ended, a prepolymer was obtained. After the above prepolymer was cooled to room temperature, a latent siloxane curing agent with a branching degree of 0.85 and R being was added thereto (25 parts by mass), and a one-component polyurea coating was obtained by stirring. The one-component polyurea coating was dropped onto the substrate by a drop-coating method, and after curing at room temperature for 24 h, a transparent wear-resistant and temperature-resistant protective coating for electronic products was obtained. The specific properties of the transparent wear-resistant and temperature-resistant protective coating for electronic products are shown in Table 1.

[0040] Example 3

[0041] Isophorone diisocyanate (50 parts by mass), perfluoropolyether alcohol with a molecular weight of 1700 (1.5 parts by mass), and dibutyltin dilaurate (1.5 parts by mass) were respectively added into a clean reaction flask. Then ethyl acetate (850 parts by mass) was added, and the mixture was placed in an ice-water bath at 0 °C. Polyetheramine D400 (50 parts by mass) was slowly added dropwise. After the addition was completed, the mixture was reacted at room temperature for 5 h, then heated to 70 °C and kept at this temperature for 5 h. After the reaction ended, a prepolymer was obtained. After the above prepolymer was cooled to room temperature, a latent siloxane curing agent with a branching degree of 0.85 and R being was added thereto (25 parts by mass), and a one-component polyurea coating was obtained by stirring. The one-component polyurea coating was dropped onto the substrate by a drop-coating method, and after curing at room temperature for 24 h, a transparent wear-resistant and temperature-resistant protective coating for electronic products was obtained. The specific properties of the transparent wear-resistant and temperature-resistant protective coating for electronic products are shown in Table 1.

[0042] Example 4

[0043] Isophorone diisocyanate (50 parts by mass), perfluoropolyether alcohol with a molecular weight of 1700 (1.5 parts by mass), and dibutyltin dilaurate (1.5 parts by mass) were respectively added into a clean reaction flask. Then ethyl acetate (850 parts by mass) was added, and the mixture was placed in an ice-water bath at 0 °C. Polyetheramine D230 (25 parts by mass) was slowly added dropwise. After the addition was completed, the mixture was reacted at room temperature for 5 h, then heated to 70 °C and kept at this temperature for 5 h. After the reaction ended, a prepolymer was obtained. After the above prepolymer was cooled to room temperature, a latent siloxane curing agent with a branching degree of 0.85 and R being The latent silicone curing agent (25 parts by mass) was added and stirred to obtain a one-component polyurea coating.

[0044] The one-component polyurea coating was drop-coated onto a substrate and cured at room temperature for 24 h to obtain a transparent, wear-resistant, and temperature-resistant protective coating for electronic products. The specific properties of the transparent, wear-resistant, and temperature-resistant protective coating for electronic products are shown in Table 1.

[0045] Example 5

[0046] Isophorone diisocyanate (50 parts by mass), perfluoropolyether alcohol with a molecular weight of 1700 (1.5 parts by mass), and dibutyltin dilaurate (1.5 parts by mass) were respectively added into a clean reaction flask. Then ethyl acetate (850 parts by mass) was added, and the mixture was placed in an ice-water bath at 0 °C. Polyetheramine D400 (25 parts by mass) and D230 (12.5 parts by mass) were slowly added dropwise. After the addition was completed, the mixture was reacted at room temperature for 5 h, then heated to 70 °C and kept at this temperature for 5 h. After the reaction ended, a prepolymer was obtained. After the above prepolymer was cooled to room temperature, a latent silicone curing agent with a branching degree of 0.85 and R being was added (25 parts by mass), and stirred to obtain a one-component polyurea coating. The one-component polyurea coating was drop-coated onto a substrate and cured at room temperature for 24 h to obtain a transparent, wear-resistant, and temperature-resistant protective coating for electronic products. The specific properties of the transparent, wear-resistant, and temperature-resistant protective coating for electronic products are shown in Table 1.

[0047] Example 6

[0048] Isophorone diisocyanate (50 parts by mass), perfluoropolyether alcohol with a molecular weight of 1700 (1.5 parts by mass), and dibutyltin dilaurate (1.5 parts by mass) were respectively added into a clean reaction flask. Then ethyl acetate (850 parts by mass) was added, and the mixture was placed in an ice-water bath at 0 °C. Polyetheramine D400 (25 parts by mass), D230 (2.5 parts by mass), and D2000 (1 part by mass) were slowly added dropwise. After the addition was completed, the mixture was reacted at room temperature for 5 h, then heated to 70 °C and kept at this temperature for 5 h. After the reaction ended, a prepolymer was obtained. After the above prepolymer was cooled to room temperature, a latent silicone curing agent with a branching degree of 0.85 and R being was added (25 parts by mass), and stirred to obtain a one-component polyurea coating. The one-component polyurea coating was drop-coated onto a substrate and cured at room temperature for 24 h to obtain a transparent, wear-resistant, and temperature-resistant protective coating for electronic products. The specific properties of the transparent, wear-resistant, and temperature-resistant protective coating for electronic products are shown in Table 1.

[0049] Example 7

[0050] Hexamethylene diisocyanate (40 parts by mass), perfluoropolyether alcohol with a molecular weight of 1700 (1.5 parts by mass), and stannous octoate (1.5 parts by mass) were respectively added into a clean reaction flask. Then, chloroform (850 parts by mass) was added, and the mixture was placed in an ice-water bath at 0 °C. Polyetheramine D400 (50 parts by mass) was slowly added dropwise. After the addition was completed, the reaction was carried out at room temperature for 5 h, and then the temperature was raised to 70 °C and kept for 5 h. After the reaction ended, a prepolymer was obtained. When the above prepolymer was cooled to room temperature, a latent siloxane curing agent with a branching degree of 0.85 and R being was added thereto (25 parts by mass), and a one-component polyurea coating was obtained by stirring. The one-component polyurea coating was dropped onto the substrate by a drop-coating method, and after curing at room temperature for 24 h, a transparent, wear-resistant, and temperature-resistant protective coating for electronic products was obtained. The specific properties of this transparent, wear-resistant, and temperature-resistant protective coating for electronic products are shown in Table 1.

[0051] Example 8

[0052] Isophorone diisocyanate (50 parts by mass), perfluoropolyether alcohol with a molecular weight of 1000 (1.5 parts by mass), and dibutyltin dilaurate (1.5 parts by mass) were respectively added into a clean reaction flask. Then, chloroform (850 parts by mass) was added, and the mixture was placed in an ice-water bath at 0 °C. Polyetheramine D400 (50 parts by mass) was slowly added dropwise. After the addition was completed, the reaction was carried out at room temperature for 5 h, and then the temperature was raised to 70 °C and kept for 5 h. After the reaction ended, a prepolymer was obtained. When the above prepolymer was cooled to room temperature, a latent siloxane curing agent with a branching degree of 0.85 and R being was added thereto (25 parts by mass), and a one-component polyurea coating was obtained by stirring. The one-component polyurea coating was dropped onto the substrate by a spraying method, and after curing at room temperature for 24 h, a transparent, wear-resistant, and temperature-resistant protective coating for electronic products was obtained. The specific properties of this transparent, wear-resistant, and temperature-resistant protective coating for electronic products are shown in Table 1.

[0053] Example 9

[0054] Isophorone diisocyanate (50 parts by mass), perfluoropolyether alcohol with a molecular weight of 1700 (1.5 parts by mass), and dibutyltin dilaurate (1.5 parts by mass) were respectively added into a clean reaction flask. Then, ethyl acetate (850 parts by mass) was added, and the mixture was placed in an ice-water bath at 0 °C. Polyetheramine D400 (50 parts by mass) was slowly added dropwise. After the addition was completed, the reaction was carried out at room temperature for 5 h, and then the temperature was raised to 70 °C and kept for 5 h. After the reaction ended, a prepolymer was obtained. When the above prepolymer was cooled to room temperature, a latent siloxane curing agent with a branching degree of 0.6 and R being was added thereto (25 parts by mass), and a one-component polyurea coating was obtained by stirring. The one-component polyurea coating was dropped onto the substrate by a drop-coating method, and after curing at room temperature for 24 h, a transparent, wear-resistant, and temperature-resistant protective coating for electronic products was obtained. The specific properties of this transparent, wear-resistant, and temperature-resistant protective coating for electronic products are shown in Table 1.

[0055] Comparative Example 1

[0056] Isophorone diisocyanate (50 parts by mass) and dibutyltin dilaurate (1.5 parts by mass) were respectively added into a clean reaction flask. Then ethyl acetate (850 parts by mass) was added, and the mixture was placed in an ice-water bath at 0 °C. Polyetheramine D400 (50 parts by mass) was slowly added dropwise. After the addition was completed, the reaction was carried out at room temperature for 5 h, then the temperature was raised to 70 °C and kept for 5 h. After the reaction was completed, a prepolymer was obtained. After the above prepolymer was cooled to room temperature, a latent siloxane curing agent with a branching degree of 0.85 and R as was added thereto (25 parts by mass), and a one-component polyurea coating was obtained by stirring. The one-component polyurea coating was dropped onto the substrate by a drop-coating method, and after curing at room temperature for 24 h, a transparent wear-resistant room-temperature-curing electronic protective coating was obtained. The specific properties of the transparent wear-resistant and temperature-resistant electronic product protective coating are shown in Table 1.

[0057] Comparative Example 2

[0058] Hexamethylene diisocyanate (40 parts by mass), perfluoropolyether alcohol with a molecular weight of 1700 (1.5 parts by mass), and stannous octoate (1.5 parts by mass) were respectively added into a clean reaction flask. Then chloroform (850 parts by mass) was added, and the mixture was placed in an ice-water bath at 0 °C. Polyetheramine D400 (100 parts by mass) was slowly added dropwise. After the addition was completed, the reaction was carried out at room temperature for 5 h, then the temperature was raised to 70 °C and kept for 5 h. After the reaction was completed, a polyurea coating was obtained. The polyurea coating was dropped onto the substrate by a drop-coating method, and after curing at room temperature for 24 h, an electronic protective coating was obtained. The specific properties of the electronic protective coating are shown in Table 1.

[0059] The water contact angle, transparency, pencil hardness and velvet cloth abrasion resistance test results of the transparent wear-resistant and temperature-resistant electronic product protective coatings obtained in the above examples are shown in Table 1 below.

[0060] Table 1

[0061]

[0062] As mentioned above, it is only the preferred embodiment of the present invention, so the scope of implementation of the present invention cannot be limited thereby. That is, equivalent changes and modifications made according to the scope of the present invention patent and the content of the specification should still fall within the scope covered by the present invention.

Claims

1. A transparent, wear-resistant and temperature-resistant protective coating for electronic products, Characterized in that: It is composed of a prepolymer and a latent silicone curing agent, The prepolymer is prepared by mixing perfluoropolyether alcohol, diisocyanate compound, composite polyetheramine, metal catalyst and organic solvent; The structural formula of perfluoropolyether alcohol is n = 1 - 10; The structural formula of the latent silicone curing agent is R is Its degree of branching is 0.6 - 0.85; The mass ratio of perfluoropolyether alcohol, diisocyanate compound, composite polyetheramine, metal catalyst, organic solvent and latent silicone curing agent is 1.5 - 3:50 - 100:0 - 50:1.5 - 3:100 - 800:10 - 100.

2. A transparent, wear-resistant and temperature-resistant protective coating for electronic products according to claim 1, Characterized in that: The prepolymer is prepared by mixing perfluoropolyether alcohol, diisocyanate compound, composite polyetheramine, metal catalyst and organic solvent in a mass ratio of 1.5 - 3:50 - 100:0 - 50:1.5 - 3:100 - 800.

3. A transparent, wear-resistant and temperature-resistant protective coating for electronic products according to claim 2, Characterized in that: The preparation method of the prepolymer includes: adding a certain amount of perfluoropolyether alcohol, metal catalyst and diisocyanate compound into a clean reaction kettle, slowly dropping the composite polyetheramine while stirring at 0 - 10°C, and controlling the temperature to react at 0 - 10°C for 1 - 3 hours and then raising the temperature to 60 - 90°C, and then keeping the temperature for reaction for 4 - 8 hours to obtain it.

4. A transparent, wear-resistant and temperature-resistant protective coating for electronic products according to claim 1, Characterized in that: The composite polyetheramine is at least one of D230, D400 and D2000.

5. A transparent, wear-resistant and temperature-resistant protective coating for electronic products according to claim 1, Characterized in that: The metal catalyst is at least one of potassium acetate, potassium octoate, potassium oleate, stannous octoate and dibutyltin dilaurate.

6. A transparent, wear-resistant and temperature-resistant protective coating for electronic products according to claim 1, Characterized in that: The diisocyanate compound is at least one of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.

7. A transparent, wear-resistant and temperature-resistant protective coating for electronic products according to claim 1, Characterized in that: The organic solvent is a ketone organic solvent, an ester organic solvent, a fluorine organic solvent or a chlorine organic solvent.

8. A transparent, wear-resistant and temperature-resistant protective coating for electronic products according to claim 7, Characterized in that: The ketone organic solvent is at least one of acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; the ester organic solvent is at least one of methyl acetate, ethyl acetate, propyl acetate and butyl acetate; the fluorine organic solvent is at least one of 2-(trifluoromethyl)-3-ethoxydodecafluorohexane, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-trifluoromethylpentane, 1,1,1,2,2,3,3,4,4,4-nonafluoro-4-ethoxybutane, 1,1,1,2,2,3,3,4,4,4-nonafluoro-4-methoxybutane, 1,1,1,2,3,3-hexafluoro-3-(2,2,2-trifluoroethoxy)propane or 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether, hexafluoropropylene dimer, hexafluoropropylene trimer, 2H,3H-decafluoropentane, hexadecafluoroheptane and octadecafluorooctane; the chlorine organic solvent is dichloromethane and / or chloroform.

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