Polycarbonate composite coating for improving film surface adhesion and preparation method thereof

Abstract

The invention discloses a polycarbonate composite coating capable of improving film surface adhesion. The composite coating is prepared from the following raw materials: polycarbonate resin, a tackifier, nano filler, a compatilizer, an antioxidant, an anti-ultraviolet agent and a solvent. The invention also provides a preparation method of the polycarbonate composite coating, which comprises the following steps: adding the raw materials into a reaction kettle according to a certain sequence, and dissolving and crosslinking under a high-temperature condition to prepare the polycarbonate composite coating. The adhesion of the polycarbonate composite coating on the surface of a film is improved by adding the tackifier, meanwhile, the high-temperature and high-humidity resistance of the polycarbonate composite coating is improved by adding the nano coating, and the polycarbonate composite coating has a good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of thin film technology and relates to a polycarbonate composite coating for improving the adhesion of thin film surfaces and its preparation method. Background Technology

[0002] Polycarbonate is an important engineering plastic, widely used in various fields due to its excellent transparency, toughness, heat resistance, and superior processing performance. Polycarbonate composite coatings contain ester groups in their chemical structure and are typically polymerized from bisphenol A and carbonates. With technological advancements, the application areas of polycarbonate composite coatings continue to expand. Electronic materials often use special thin film materials, such as PI (polyimide) films, PS (polystyrene) films, and PC (polycarbonate) films, which are relatively difficult to adhere to. In practical applications, due to various external forces such as extrusion, humidity, or high temperatures, the adhesion between these thin film materials and surface coatings decreases, easily leading to peeling and detachment. Therefore, to improve film surface adhesion, a coating layer needs to be applied first, followed by electroplating or other processes. Due to its excellent properties, polycarbonate composite coatings play a crucial role in improving film surface adhesion. Summary of the Invention

[0003] The purpose of this invention is to provide a polycarbonate composite coating and its preparation method for improving the adhesion of thin film surfaces. By adding a tackifier, the adhesion of the polycarbonate composite coating is improved, and at the same time, the high temperature and high humidity resistance of the polycarbonate composite coating is enhanced, which has good application prospects.

[0004] The objective of this invention can be achieved through the following technical solutions: A polycarbonate composite coating for improving the adhesion of thin film surfaces, wherein the raw materials of the polycarbonate composite coating include: 95-105 parts polycarbonate resin, 8-14 parts tackifier, 3-5 parts nanofiller, 2-5 parts compatibilizer, 0.5-1 part antioxidant and 0.5-1 part UV stabilizer and 150-200 parts solvent.

[0005] Furthermore, the tackifier is composed of modified polyether ether ketone and polyether ester in a mass ratio of 1:0.4-0.5.

[0006] Further, the modified polyether ether ketone is prepared according to the following steps: Polyetheretherketone (PEEK) and difluoromethane were mixed at a ratio of 1:7-9 g / mL, heated to 60-80℃, and stirred until dissolved. Then, maleic anhydride (9-11% of the mass of PEEK) was added, stirred until dissolved, heated to 160-180℃, and kept at this temperature for 2-3 hours. After the temperature was maintained, the mixture was cooled to room temperature and poured into 5℃ cold water to form a precipitate. The precipitate was collected, washed three times with deionized water, and dried at 80℃ for 12 hours to obtain modified PEEK.

[0007] Furthermore, the nanofiller is composed of nano-silica and modified nano-montmorillonite in a mass ratio of 0.5-0.6:0.37-0.43; the average particle size of the nano-silica is 30-50 nm.

[0008] Furthermore, the modified nano-montmorillonite is prepared according to the following steps: Montmorillonite, hexadecyltrimethylammonium bromide, and deionized water were mixed in a mass ratio of 1:1.1-1.3:3 and stirred for 22-28 hours. The mixture was then passed through a 300-mesh filter cloth to obtain a solid. After rinsing with deionized water three times, the solid was dried at 60°C for 12 hours to obtain a powder. The powder was then pulverized to 30-70 nm to obtain modified nano-montmorillonite.

[0009] Furthermore, the compatibilizer is maleic anhydride-grafted polyolefin.

[0010] Furthermore, the solvent is two or more of N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and cyclohexanone.

[0011] Furthermore, the preparation steps of the polycarbonate composite coating include the following steps: S1. Add 2 / 3 of the solvent to the reactor, then add polycarbonate resin and thickener. Heat to 60-70℃ and stir until completely dissolved to obtain material one. S2. Add nanofiller, compatibilizer, antioxidant, UV stabilizer and the remaining solvent to material one, stir for 30-60 minutes to obtain material two; S3. Cool the material to room temperature and filter it to obtain the polycarbonate composite coating.

[0012] The beneficial effects of this invention are: (1) The present invention prepares a tackifier by mixing modified polyether ether ketone and polyether ester. The modified polyether ether ketone introduces polar groups through a grafting reaction, which enhances its compatibility in polycarbonate composite coatings. An adhesive layer is formed at the interface between polycarbonate and other materials, which enhances the adhesion between polycarbonate and other materials and improves the interface strength, thereby effectively preventing material peeling and failure. The addition of polyether ester can improve the impact strength of polycarbonate, reduce the risk of brittle fracture, and effectively reduce the solution viscosity of composite coatings, improve the fluidity of coatings, thereby promoting the uniform dispersion of other materials, improving the compatibility between materials, and thus synergistically improving adhesion.

[0013] (2) The present invention adds nanofillers, in which the high specific surface area of ​​nano silica makes it uniformly dispersed in polycarbonate composite coatings, enhancing the rigidity and strength of the material. The layered structure of modified nano montmorillonite can effectively enhance the barrier properties of the material. The synergy of the two can effectively prevent the propagation of microcracks and improve the impact resistance of the coating.

[0014] (3) The present invention improves the adhesion of polycarbonate composite coating by adding tackifier, and at the same time introduces nanofillers to improve the high temperature and high humidity resistance of polycarbonate composite coating, which has good application prospects. Detailed Implementation

[0015] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with embodiments, is provided below.

[0016] In all embodiments and comparative examples of this invention, the polycarbonate resin was purchased directly from the market from Shanghai Yisufa New Material Co., Ltd.; the polyetheretherketone was purchased directly from the market from Shanghai Xiangsu New Material Co., Ltd.; the difluoromethane was purchased directly from the market from Anhui Jinyueguan New Material Technology Co., Ltd.; the maleic anhydride was purchased directly from the market from Jinan Fuhao Chemical Co., Ltd.; the polyether ester was purchased directly from the market from Dongguan Tianzhihong Plastics Co., Ltd.; and the nano silica was purchased directly from the market. The following materials were purchased directly from the market: Montmorillonite, N,N-dimethylformamide, and dimethyl sulfoxide from Qinghe County Ruijiang Metal Materials Co., Ltd.; hexadecyltrimethylammonium bromide from Shandong Guohua Chemical Co., Ltd.; maleic anhydride-grafted polyolefin from Shanghai Yiding Plastics Co., Ltd.; 2,6-di-tert-butyl-4-methylphenol from Hubei Weishi Chemical Reagent Co., Ltd.; and the UV stabilizer Tinuvin 384-2 from Shanghai Kaiyin Chemical Co., Ltd.

[0017] Example 1 A polycarbonate composite coating for improving film surface adhesion, wherein the raw materials of the polycarbonate composite coating in this embodiment include: 95 parts polycarbonate resin, 8 parts tackifier, 3 parts nanofiller, 2 parts compatibilizer, 0.5 parts antioxidant, 0.5 parts UV stabilizer and 150 parts solvent.

[0018] The antioxidant in this embodiment is 2,6-di-tert-butyl-4-methylphenol; the UV stabilizer is Tinuvin 384-2.

[0019] The tackifier in this embodiment is composed of modified polyether ether ketone and polyether ester in a mass ratio of 1:0.4-0.5.

[0020] The modified polyetheretherketone in this embodiment was prepared according to the following steps: Polyetheretherketone (PEEK) and difluoromethane were mixed at a ratio of 1:7 g / mL, heated to 60°C, and stirred until dissolved. Then, maleic anhydride (9% by mass of PEEK) was added and stirred until dissolved. The mixture was heated to 160°C and kept at that temperature for 2 hours. After the heating was completed, the mixture was cooled to room temperature and poured into 5°C cold water to form a precipitate. The precipitate was collected, washed three times with deionized water, and dried at 80°C for 12 hours to obtain modified PEEK.

[0021] The nanofiller in this embodiment is composed of nano-silica and modified nano-montmorillonite in a mass ratio of 0.5:0.37; the average particle size of the nano-silica is 30 nm.

[0022] The modified nano-montmorillonite in this embodiment was prepared according to the following steps: Montmorillonite, hexadecyltrimethylammonium bromide, and deionized water were mixed in a mass ratio of 1:1.1:3 and stirred for 22 hours. The mixture was then passed through a 300-mesh filter cloth to obtain a solid. After being washed three times with deionized water, the solid was dried at 60°C for 12 hours to obtain a powder. The powder was then pulverized to 30 nm to obtain modified nano-montmorillonite.

[0023] The compatibilizer in this embodiment is maleic anhydride-grafted polyolefin.

[0024] The solvent in this embodiment is obtained by mixing N,N-dimethylformamide and dimethyl sulfoxide in a mass ratio of 1:1.

[0025] The preparation steps of the polycarbonate composite coating in this embodiment include the following steps: S1. Add 2 / 3 of the solvent to the reaction vessel, then add polycarbonate resin and thickener. Heat to 60°C and stir until completely dissolved to obtain material one. S2. Add nanofiller, compatibilizer, antioxidant, UV stabilizer and the remaining solvent to material one, stir for 30 minutes to obtain material two; S3. Cool the material to room temperature and filter it to obtain the polycarbonate composite coating.

[0026] Example 2 A polycarbonate composite coating for improving film surface adhesion, wherein the raw materials of the polycarbonate composite coating in this embodiment include: 105 parts polycarbonate resin, 14 parts tackifier, 5 parts nanofiller, 5 parts compatibilizer, 1 part antioxidant, 1 part UV stabilizer and 175 parts solvent.

[0027] The antioxidant in this embodiment is 2,6-di-tert-butyl-4-methylphenol; the UV stabilizer is Tinuvin 384-2.

[0028] The tackifier in this embodiment is composed of modified polyether ether ketone and polyether ester in a mass ratio of 1:0.4-0.5.

[0029] The modified polyetheretherketone in this embodiment was prepared according to the following steps: Polyetheretherketone (PEEK) and difluoromethane were mixed at a ratio of 1:9 g / mL, heated to 80°C, and stirred until dissolved. Then, maleic anhydride (11% of the mass of PEEK) was added and stirred until dissolved. The mixture was heated to 180°C and kept at that temperature for 3 hours. After the heating was completed, the mixture was cooled to room temperature and poured into 5°C cold water to form a precipitate. The precipitate was collected, washed three times with deionized water, and dried at 80°C for 12 hours to obtain modified PEEK.

[0030] The nanofiller in this embodiment is composed of nano-silica and modified nano-montmorillonite in a mass ratio of 0.6:0.43; the average particle size of the nano-silica is 50 nm.

[0031] The modified nano-montmorillonite in this embodiment was prepared according to the following steps: Montmorillonite, hexadecyltrimethylammonium bromide, and deionized water were mixed in a mass ratio of 1:1.3:3 and stirred for 28 hours. The mixture was then passed through a 300-mesh filter cloth to obtain a solid. After being washed three times with deionized water, the solid was dried at 60°C for 12 hours to obtain a powder. The powder was then pulverized to 70 nm to obtain modified nano-montmorillonite.

[0032] The compatibilizer in this embodiment is maleic anhydride-grafted polyolefin.

[0033] The solvent in this embodiment is obtained by mixing N,N-dimethylformamide and dimethyl sulfoxide in a mass ratio of 1:1.

[0034] The preparation steps of the polycarbonate composite coating in this embodiment include the following steps: S1. Add 2 / 3 of the solvent to the reaction vessel, then add polycarbonate resin and thickener. Heat to 65°C and stir until completely dissolved to obtain material one. S2. Add nanofiller, compatibilizer, antioxidant, UV stabilizer and the remaining solvent to material one, stir for 45 minutes to obtain material two; S3. Cool the material to room temperature and filter it to obtain the polycarbonate composite coating.

[0035] Example 3 A polycarbonate composite coating for improving film surface adhesion, wherein the raw materials of the polycarbonate composite coating in this embodiment include: 100 parts polycarbonate resin, 11 parts tackifier, 4 parts nanofiller, 3.5 parts compatibilizer, 0.75 parts antioxidant, 0.75 parts UV stabilizer and 200 parts solvent.

[0036] The antioxidant in this embodiment is 2,6-di-tert-butyl-4-methylphenol; the UV stabilizer is Tinuvin 384-2.

[0037] The tackifier in this embodiment is composed of modified polyether ether ketone and polyether ester in a mass ratio of 1:0.45.

[0038] The modified polyetheretherketone in this embodiment was prepared according to the following steps: Polyetheretherketone (PEEK) and difluoromethane were mixed at a ratio of 1:8 g / mL, heated to 70°C, and stirred until dissolved. Then, maleic anhydride (10% of the mass of PEEK) was added and stirred until dissolved. The mixture was heated to 170°C and kept at that temperature for 2.5 hours. After the temperature was maintained, the mixture was cooled to room temperature and poured into 5°C cold water to form a precipitate. The precipitate was collected, washed three times with deionized water, and dried at 80°C for 12 hours to obtain modified PEEK.

[0039] The nanofiller in this embodiment is composed of nano-silica and modified nano-montmorillonite in a mass ratio of 0.55:0.4; the average particle size of the nano-silica is 40 nm.

[0040] The modified nano-montmorillonite in this embodiment was prepared according to the following steps: Montmorillonite, hexadecyltrimethylammonium bromide, and deionized water were mixed in a mass ratio of 1:1.2:3 and stirred for 25 hours. The mixture was then passed through a 300-mesh filter cloth to obtain a solid. After being washed three times with deionized water, the solid was dried at 60°C for 12 hours to obtain a powder. The powder was then pulverized to 30-70 nm to obtain modified nano-montmorillonite.

[0041] The compatibilizer in this embodiment is maleic anhydride-grafted polyolefin.

[0042] The solvent in this embodiment is obtained by mixing N,N-dimethylformamide and dimethyl sulfoxide in a mass ratio of 1:1.

[0043] The preparation steps of the polycarbonate composite coating in this embodiment include the following steps: S1. Add 2 / 3 of the solvent to the reaction vessel, then add polycarbonate resin and thickener. Heat to 70°C and stir until completely dissolved to obtain material one. S2. Add nanofiller, compatibilizer, antioxidant, UV stabilizer and the remaining solvent to material one, stir for 60 minutes to obtain material two; S3. Cool the material to room temperature and filter it to obtain the polycarbonate composite coating.

[0044] Comparative Example 1 Based on Example 3, the modified polyether ether ketone in the tackifier was removed and replaced with an equal weight of polyether ether ketone, while other conditions remained the same as in Example 3.

[0045] Comparative Example 2 Based on Example 3, the modified polyether ether ketone in the tackifier was removed and replaced with an equal weight of polyether ester, while other conditions remained the same as in Example 3.

[0046] Comparative Example 3 Based on Example 3, the polyether ester in the tackifier was removed and replaced with an equal weight of modified polyether ether ketone, while other conditions remained the same as in Example 3.

[0047] Comparative Example 4 Based on Example 3, the nano-silica in the nanofiller was removed and replaced with an equal weight of modified nano-montmorillonite, while other conditions remained the same as in Example 3.

[0048] Comparative Example 5 Based on Example 3, the modified nano-montmorillonite in the nanofiller was removed and replaced with an equal weight of nano-silica, while other conditions remained the same as in Example 3.

[0049] Comparative Example 6 Based on Example 3, the modified nano-montmorillonite in the nanofiller was removed and replaced with an equal weight of nano-montmorillonite, while other conditions remained the same as in Example 3.

[0050] Comparative Example 7 Based on Example 3, while keeping other conditions consistent, the modified nano-montmorillonite in the nanofiller was removed and replaced with an equal weight of modified montmorillonite, wherein the modified montmorillonite was prepared according to the following steps: Montmorillonite, hexadecyltrimethylammonium bromide, and deionized water were mixed in a mass ratio of 1:1.2:3 and stirred for 25 hours. The mixture was then passed through a 300-mesh filter cloth to obtain a solid. After rinsing with deionized water three times, the solid was dried at 60°C for 12 hours to obtain modified montmorillonite.

[0051] Performance testing: (1) Adhesion test: The polycarbonate composite coatings prepared in Examples 1-3 and Comparative Examples 1-7 were coated on 25μm PI films respectively. When coating, the dry coating amount should be kept at 2~3μm. After drying, the adhesion test was carried out according to the standard GB / T9286-2021. The smaller the grade, the better the adhesion. (2) High temperature and high humidity resistance test: After aging in a test chamber at 85℃ and 85% relative humidity for 96 hours, the coated sample is taken out and then the adhesion test is carried out according to the standard GB / T 9286-2021. The smaller the grade, the better the adhesion.

[0052] As shown in Table 1, the adhesion of polycarbonate composite coatings to the film surface and their resistance to high temperature and high humidity can be improved by introducing tackifiers and adding nanofillers.

[0053] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any indirect modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A polycarbonate composite coating for improving the adhesion of a thin film surface, characterized in that: The raw materials for the polycarbonate composite coating include: 95-105 parts polycarbonate resin, 8-14 parts tackifier, 3-5 parts nanofiller, 2-5 parts compatibilizer, 0.5-1 part antioxidant and 0.5-1 part UV stabilizer and 150-200 parts solvent.

2. The polycarbonate composite coating for improving film surface adhesion according to claim 1, characterized in that: The thickener is composed of modified polyether ether ketone and polyether ester in a mass ratio of 1:0.4-0.

5.

3. The polycarbonate composite coating for improving film surface adhesion according to claim 2, characterized in that: The modified polyether ether ketone was prepared according to the following steps: Polyetheretherketone (PEEK) and difluoromethane were mixed at a ratio of 1:7-9 g / mL, heated to 60-80℃, and stirred until dissolved. Then, maleic anhydride (9-11% of the mass of PEEK) was added, stirred until dissolved, heated to 160-180℃, and kept at this temperature for 2-3 hours. After the temperature was maintained, the mixture was cooled to room temperature and poured into 5℃ cold water to form a precipitate. The precipitate was collected, washed three times with deionized water, and dried at 80℃ for 12 hours to obtain modified PEEK.

4. The polycarbonate composite coating for improving film surface adhesion according to claim 1, characterized in that: The nanofiller is composed of nano-silica and modified nano-montmorillonite in a mass ratio of 0.5-0.6:0.37-0.43; the average particle size of the nano-silica is 30-50 nm.

5. The polycarbonate composite coating for improving film surface adhesion according to claim 4, characterized in that: The modified nano-montmorillonite was prepared according to the following steps: Montmorillonite, hexadecyltrimethylammonium bromide, and deionized water were mixed in a mass ratio of 1:1.1-1.3:3 and stirred for 22-28 hours. The mixture was then passed through a 300-mesh filter cloth to obtain a solid. After rinsing with deionized water three times, the solid was dried at 60°C for 12 hours to obtain a powder. The powder was then pulverized to 30-70 nm to obtain modified nano-montmorillonite.

6. The polycarbonate composite coating for improving film surface adhesion according to claim 1, characterized in that: The compatibilizer is maleic anhydride-grafted polyolefin.

7. The polycarbonate composite coating for improving film surface adhesion according to claim 1, characterized in that: The solvent is two or more of N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and cyclohexanone.

8. A method for preparing a polycarbonate composite coating for improving film surface adhesion as described in any one of claims 1-7, characterized in that: The preparation steps of the polycarbonate composite coating include the following steps: S1. Add 2 / 3 of the solvent to the reactor, then add polycarbonate resin and thickener, heat to 60-70℃ and stir until completely dissolved to obtain material one; S2. Add nanofiller, compatibilizer, antioxidant, UV stabilizer and the remaining solvent to material one, stir for 30-60 minutes to obtain material two; S3. Cool the material to room temperature and filter it to obtain the polycarbonate composite coating.

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