Epoxy barrier film and preparation method thereof

Abstract

The invention belongs to the technical field of composite films, and particularly discloses an epoxy barrier film and a preparation method thereof.The epoxy barrier film comprises a substrate and a film layer coated and photocured on the substrate, and the film layer is prepared from, by weight, 70-96 parts of long-carbon-chain epoxy resin, 0-25 parts of epoxy organosilane and 1-6 parts of photoinitiator. And 0.25 to 0.75 part of a leveling agent. The preparation method comprises the following steps: mixing epoxy resin with a long carbon chain, epoxy organosilane, a photoinitiator and a flatting agent according to a certain proportion, uniformly stirring, coating on a substrate to form a film, and carrying out light-induced self-assembly curing to obtain the epoxy barrier film. The polymer crystal is introduced into the polymer film in situ through a self-assembly structure formed in the photo-initiation polymerization process of the epoxy resin, so that the prepared film is high in water vapor barrier property and good in mechanical property, and the preparation process is simple, energy-saving and environment-friendly and has a wide application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite films, and relates to a polymer barrier film, specifically to an epoxy barrier film and a preparation method thereof. Background Art

[0002] Barrier films are an important type of functional material and are widely used in fields such as food packaging, electronic packaging, and medical devices. Polymer barrier films have attracted wide attention due to their advantages such as low density, low price, easy processing, and corrosion resistance. However, compared with traditional metal film packaging materials, they have disadvantages such as poor barrier effects on substances such as moisture, oxygen, and organic small molecules, low mechanical strength, and insufficient heat resistance, which greatly hinder the application of polymer barrier films in high-end packaging fields such as OLED, LCD, and vacuum insulation.

[0003] Based on the molecular detour theory, introducing inorganic reinforcing agents such as layered silicates and layered hydrotalcites for reinforcement is a very economical and effective means to improve the barrier performance of polymer membrane materials. The Toyota Research Center in Japan first studied the permeation of water vapor in a series of nylon 6-montmorillonite nanocomposites and found that the permeation rate decreased with the increase in the amount of montmorillonite used. However, it is often difficult to achieve good dispersion of such hydrophilic inorganic lamellar reinforcing materials in polymer polymers, seriously interfering with the gas barrier performance of the composites. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an epoxy barrier film. The present invention endows it with high barrier properties and mechanical strength by regulating the self-assembled structure during the photoinitiated polymerization of epoxy resin and in-situ introducing polymer crystals into the polymer. Another purpose of the present invention is to provide a preparation method for the epoxy barrier film, and the method of the present invention is simple to operate, energy-saving, and environmentally friendly.

[0005] The present invention is achieved through the following technical solutions:

[0006] An epoxy barrier film, comprising a substrate and a film layer coated and photocured on the substrate. The film layer is composed of the following components in parts by weight: 70-96 parts of long-chain epoxy resin, 0-25 parts of epoxy organosilane, 1-6 parts of photoinitiator, and 0.25-0.75 parts of leveling agent.

[0007] A further improvement of the present invention is as follows:

[0008] The long-chain epoxy resin is one or a combination of two or more of 1,2-epoxyoctadecane, 1,2-epoxyhexadecane, 1,2-epoxytetradecane, 1,2-epoxydodecane, 1,2-epoxydecane, 1,2-epoxyoctane, or 1,2,7,8-diepoxyoctane.

[0009] Further, the epoxy organosilane is one or a combination of two or more of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, diethoxy(3-glycidoxypropyl)methylsilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane or 5,6-epoxyhexyltriethoxysilane.

[0010] Further, the photoinitiator is one or a combination of two or more of bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylbenzene)iodonium hexafluoroantimonate, 4-octyloxydiphenyliodonium hexafluoroantimonate or 2-methyl-α-[2-[[propylsulfonyl]imine]-3(2H)-thiophenemethylene]-benzeneacetonitrile.

[0011] Further, the leveling agent is BYK333.

[0012] Further, the substrate is selected from PET, PVC or BOPP.

[0013] A further improvement of the present invention is as follows:

[0014] A method for preparing an epoxy barrier film, comprising the following steps:

[0015] Step 1: Weigh a certain amount of long-chain epoxy resin, epoxy organosilane, photoinitiator and leveling agent at room temperature, and stir evenly in a brown glass bottle in the dark;

[0016] Step 2: Coat the evenly stirred solution on the substrate to form a uniform liquid film;

[0017] Step 3: Place the sample prepared in Step 2 under an ultraviolet lamp at a certain temperature and air humidity for irradiation and curing to obtain an epoxy barrier film.

[0018] Further, the irradiation time of the ultraviolet lamp is 10 - 30 min.

[0019] Further, the irradiation intensity of the ultraviolet lamp is 10 - 200 mW / cm 2 .

[0020] Further, the air humidity in Step 3 is 20% - 90%.

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

[0022] (1) The present invention selects long-chain epoxy resin as a monomer, and during the polymerization process, crystals are formed by in-situ self-assembly using the van der Waals forces between long carbon chains, which are well dispersed in the polymer, thereby endowing the film with excellent barrier properties, good hydrophobic properties, and mechanical strength.

[0023] (2) Based on the principles of photocuring and self-assembly mechanisms, the present invention develops a photoinduced self-assembly process to prepare an epoxy barrier film. Not only is the regulation of polymerization conditions convenient, the polymerization efficiency high, and the production cycle significantly shortened, but also no organic solvents are used, which is energy-saving and environmentally friendly. Description of the Drawings

[0024] Figure 1 XRD pattern of the epoxy barrier film prepared in Example 1;

[0025] Figure 2 Polarizing microscope photograph of the epoxy barrier film prepared in Example 1;

[0026] It can be seen from the figure that the long-chain epoxy resin undergoes self-assembly during the photoinitiated polymerization process, partially forms polymer crystals, and is relatively uniformly dispersed in the film, realizing the construction of a microcomposite structure. Detailed Description of the Invention

[0027] The present invention will be introduced in detail below in conjunction with specific embodiments.

[0028] Example 1

[0029] In this example, an epoxy barrier film is prepared. The epoxy barrier film includes a substrate and a film layer coated and photocured on the substrate. In this example, PET is selected as the substrate, and the film layer is composed of the following components in parts by weight: 95.5 parts of 1,2-epoxyhexadecane; 4 parts of bis(dodecylphenyl)iodonium hexafluorophosphate; 0.5 part of BYK333 leveling agent.

[0030] The preparation steps are as follows:

[0031] Step 1: At room temperature, weigh a certain amount of long-chain epoxy resin, photoinitiator, and leveling agent, and stir evenly in a brown glass bottle in the dark;

[0032] Step 2: Coat the stirred solution on the substrate to form a uniform liquid film (film thickness 20 ± 2 μm);

[0033] Step 3: Place the sample prepared in Step 2 under a 50 mW / cm 2 UV lamp at 15 °C and 50% air humidity and irradiate for 30 min to obtain an epoxy barrier film.

[0034] Example 2

[0035] In this embodiment, an epoxy barrier film is prepared. The epoxy barrier film includes a substrate and a film layer coated and photocured on the substrate. In this embodiment, PET is selected as the substrate. The film layer in this embodiment is composed of the following components in parts by weight: 90.5 parts of 1,2-epoxyhexadecane; 5 parts of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; 4 parts of bis(dodecylphenyl)iodonium hexafluorophosphate; 0.5 part of BYK333 leveling agent.

[0036] The preparation steps are as follows:

[0037] Step 1: At room temperature, weigh a certain amount of long-chain epoxy resin, epoxy organosilane, photoinitiator, and leveling agent, and stir them evenly in a brown glass bottle in the dark.

[0038] Step 2: Coat the evenly stirred solution on the substrate to form a uniform liquid-phase film (film thickness 20 ± 2 μm).

[0039] Step 3: Place the sample prepared in Step 2 under a 50 mW / cm 2 UV lamp at 15 °C and 50% air humidity for 30 min to obtain the epoxy barrier film.

[0040] Example 3

[0041] In this embodiment, an epoxy barrier film is prepared. The epoxy barrier film includes a substrate and a film layer coated and photocured on the substrate. In this embodiment, PET is selected as the substrate. The film layer in this embodiment is composed of the following components in parts by weight: 80.5 parts of 1,2-epoxyhexadecane; 15 parts of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; 4 parts of bis(dodecylphenyl)iodonium hexafluorophosphate; 0.5 part of leveling agent BYK333.

[0042] The preparation steps are as follows:

[0043] Step 1: At room temperature, weigh a certain amount of long-chain epoxy resin, photoinitiator, and leveling agent, and stir them evenly in a brown glass bottle in the dark.

[0044] Step 2: Coat the evenly stirred solution on the substrate to form a uniform liquid-phase film (film thickness 20 ± 2 μm).

[0045] Step 3: Place the sample prepared in Step 2 under a 50 mW / cm 2 UV lamp at 15 °C and 50% air humidity for 30 min to obtain the epoxy barrier film.

[0046] Example 4

[0047] In this embodiment, an epoxy barrier film is prepared. The epoxy barrier film includes a substrate and a film layer coated and photocured on the substrate. In this embodiment, PET is selected as the substrate. The film layer in this embodiment is composed of the following components in parts by weight: 95.5 parts of long-chain epoxy resin (wherein, 90 parts of 1,2-epoxyhexadecane and 5.5 parts of 1,2,7,8-diepoxyoctane); 4 parts of bis(dodecylphenyl)iodonium hexafluorophosphate; 0.5 part of BYK333 leveling agent.

[0048] The preparation steps are as follows:

[0049] Step 1: At room temperature, weigh a certain amount of long-chain epoxy resin, epoxy organosilane, photoinitiator and leveling agent, and stir evenly in a brown glass bottle in the dark.

[0050] Step 2: Coat the evenly stirred solution on the substrate to form a uniform liquid film (film thickness 20 ± 2 μm).

[0051] Step 3: Place the sample prepared in Step 2 under a 50 mW / cm 2 UV lamp at 15 °C and 50% air humidity and irradiate for 20 min to obtain the epoxy barrier film.

[0052] Example 5

[0053] In this embodiment, an epoxy barrier film is prepared. The epoxy barrier film includes a substrate and a film layer coated and photocured on the substrate. In this embodiment, PET is selected as the substrate. The film layer in this embodiment is composed of the following components in parts by weight: 95.5 parts of 1,2-epoxyhexadecane; 4 parts of bis(dodecylphenyl)iodonium hexafluorophosphate; 0.5 part of BYK333 leveling agent.

[0054] The preparation steps are as follows:

[0055] Step 1: At room temperature, weigh a certain amount of long-chain epoxy resin, epoxy organosilane, photoinitiator and leveling agent, and stir evenly in a brown glass bottle in the dark.

[0056] Step 2: Coat the evenly stirred solution on the substrate to form a uniform liquid film (film thickness 20 ± 2 μm).

[0057] Step 3: Place the sample prepared in Step 2 under a 50 mW / cm 2 UV lamp at 15 °C and 20% air humidity and irradiate for 30 min to obtain the epoxy barrier film.

[0058] Example 6

[0059] In this embodiment, an epoxy barrier film is prepared. The epoxy barrier film includes a substrate and a film layer coated and photocured on the substrate. In this embodiment, PET is selected as the substrate. The film layer in this embodiment is composed of the following components in parts by weight: 90.5 parts of 1,2-epoxyoctane; 5 parts of 3-glycidoxypropyltrimethoxysilane; 4 parts of 4-octyloxydiphenyliodonium hexafluoroantimonate; 0.5 part of BYK333 leveling agent.

[0060] The preparation steps are as follows:

[0061] Step 1: At room temperature, weigh a certain amount of long-chain epoxy resin, epoxy organosilane, photoinitiator, and leveling agent, and stir evenly in a brown glass bottle in the dark.

[0062] Step 2: Coat the evenly stirred solution on the substrate to form a uniform liquid-phase film (film thickness 20 ± 2 μm).

[0063] Step 3: Place the sample prepared in Step 2 under a 10 mW / cm 2 UV lamp at 5°C and 50% air humidity for 30 min to obtain the epoxy barrier film.

[0064] The epoxy barrier films prepared in Examples 1 to 6 were tested for water contact angle, water vapor transmission rate, and pencil hardness performance. The specific methods or standards are as follows:

[0065] Water contact angle test: The wettability of the epoxy barrier film was tested using a contact angle measuring instrument model JC2000C2. The volume of deionized water dropped on the surface of the epoxy barrier film was 5.0 μL, and the contact angle was measured by the protractor method at different positions, and the average value of 5 measurements was taken.

[0066] Water vapor transmission performance test: It was carried out in accordance with the national standard GB / T 1037-2021.

[0067] Pencil hardness performance test: It was carried out in accordance with the national standard GB / T 6739-2022.

[0068] The test results of the products obtained in Examples 1 to 6 are shown in the following table, and their performance was mainly compared by the water vapor transmission amount.

[0069]

[0070] The above embodiments are only for explaining the technical concept and characteristics of the present invention, and the purpose is to enable those familiar with this technology to understand the content of the present invention and implement it accordingly, and it cannot be used to limit the protection scope of the present invention. All equivalent transformations or modifications made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. An epoxy barrier film, characterized in that, It includes a substrate and a thin film layer coated and photocured on the substrate. The thin film layer is composed of the following components in parts by weight: 70-96 parts of long-chain epoxy resin, 0-25 parts of epoxy organosilane, 1-6 parts of photoinitiator, and 0.25-0.75 parts of leveling agent.

2. An epoxy barrier film according to claim 1, characterized in that: The long-chain epoxy resin is one or a combination of two or more of 1,2-epoxyoctadecane, 1,2-epoxyhexadecane, 1,2-epoxytetradecane, 1,2-epoxydodecane, 1,2-epoxydecane, 1,2-epoxyoctane, or 1,2,7,8-diepoxyoctane.

3. An epoxy barrier film according to claim 1, characterized in that: The epoxy organosilane is one or a combination of two or more of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, diethoxy(3-glycidoxypropyl)methylsilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, or 5,6-epoxyhexyltriethoxysilane.

4. An epoxy barrier film according to claim 1, characterized in that: The photoinitiator is one or a combination of two or more of bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylbenzene)iodonium hexafluoroantimonate, 4-octyloxydiphenyliodonium hexafluoroantimonate, or 2-methyl-α-[2-[[propylsulfonyl]imine]-3(2H)-thiophenemethylene]-benzonitrile.

5. The epoxy barrier film according to claim 1, wherein: The leveling agent is BYK333.

6. The epoxy barrier film according to claim 1, characterized in that: The substrate is selected from PET, PVC, or BOPP.

7. A method for preparing an epoxy barrier film according to any one of claims 1 to 6, characterized in that, It includes the following steps: Step 1: At room temperature, weigh a certain amount of long-chain epoxy resin, epoxy organosilane, photoinitiator, and leveling agent, and stir evenly in a brown glass bottle in the dark. Step 2: Coat the evenly stirred solution on the substrate to form a uniform liquid-phase thin film. Step 3: Place the sample prepared in Step 2 under an ultraviolet lamp at a certain temperature and air humidity for irradiation and curing to obtain an epoxy barrier thin film.

8. The preparation method of an epoxy barrier film according to claim 7, wherein: The irradiation time of the ultraviolet lamp is 10-30 min.

9. The preparation method of an epoxy barrier film according to claim 7, characterized in that: The irradiation intensity of the ultraviolet lamp is 10 to 200 mW / cm 2 .

10. The preparation method of an epoxy barrier film according to claim 7, characterized in that: The air humidity in Step 3 is 20%-90%.

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