Light release force, high temperature resistant non-silicon release agent, release film and preparation method thereof

Abstract

The application discloses a light release force, high-temperature-resistant non-silicon release agent, a release film and a preparation method of the release film, and the release agent comprises the following raw material components in percentage by mass: 10-20% of epoxy resin, 5-10% of melamine resin, 1-5% of octadecylamine, 0.2-1% of an acidic catalyst and the balance of a solvent. In the application, the octadecylamine and the epoxy resin are subjected to ring-opening reaction under high-temperature conditions to form an octadecyl epoxy resin prepolymer, then, under strong acid catalysis, the -OH on the epoxy resin is reacted with the melamine resin to be cured into a film; the prepared release agent has the structures of the epoxy resin (providing adhesion, chemical resistance), the melamine resin (providing rigidity, curability, weather resistance) and the octadecylamine (providing flexibility, low release force), and the release film is endowed with low release force and temperature resistance.

Description

Technical Field

[0001] This invention relates to the field of release materials, and particularly to a non-silicone release agent with light release force and high temperature resistance, a release film, and a method for preparing the same. Background Technology

[0002] Release agents are auxiliary anti-stick coatings used in conjunction with pressure-sensitive adhesives (PSAs). Due to their unique molecular structure, release agents have low surface energy, making it difficult for substances with high surface energy, such as PSAs, to form a strong anchor and adhesion on their surface. This allows for rapid peeling with relatively low peeling force. Commonly used release films include silicone release films, fluorinated release films, and non-silicone release films. Silicone release agents are widely used due to their low surface tension and easily adjustable release force. However, with increasingly stringent requirements in the electronics industry, especially in the FPC and new energy vehicle battery fields, silicon is highly susceptible to causing malfunctions or short circuits in electronic products, making it difficult to meet usage requirements. Fluorinated release films, while offering better performance, are expensive. Non-silicone release films primarily provide anchoring force through polar groups and release force through long-chain alkanes. The curing process does not involve chemical cross-linking, resulting in poor stability under high temperature and humidity conditions, leading to coating dissolution and severely limiting their application in PSAs.

[0003] Patent CN112280085A discloses a non-silicone release agent with no silicon transfer, its application, and its preparation method. This method employs free radical polymerization and uses isocyanate for curing, ensuring the temperature resistance of the release film. However, the release force of the release layer is high and singular, making it difficult to meet the requirement of low release force during pressure-sensitive adhesive peeling.

[0004] Patent CN114014959B discloses a non-silicone release agent with adjustable release force and melting point, and its preparation method. The non-silicone release agent is prepared by a nucleophilic addition reaction between octadecyl isocyanate and polyvinyl alcohol. Post-treatment of the non-silicone release agent requires the addition of a large amount of methanol for alcohol precipitation, along with an online filtration process. It needs to be prepared and used immediately, and heated; prolonged storage can lead to powder precipitation.

[0005] Therefore, it is necessary to improve existing technologies to provide more reliable solutions. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a non-silicone release agent with light release force and high temperature resistance, a release film and its preparation method, in order to address the shortcomings of the prior art.

[0007] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: In the first aspect of the present invention, a non-silicone release agent with light release force and high temperature resistance is provided, comprising the following raw material components by mass percentage: 10%-20% epoxy resin, 5%-10% melamine resin, 1%-5% octadecylamine, 0.2%-1% acid catalyst, and 80%-95% solvent.

[0008] Preferably, the epoxy resin is at least one of bisphenol A type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin.

[0009] Preferably, the acidic catalyst is p-toluenesulfonic acid.

[0010] Preferably, the solvent is toluene.

[0011] A second aspect of the present invention provides a method for preparing the non-silicone release agent with light release force and high temperature resistance as described above, comprising the following steps:

[0012] Epoxy resin and octadecylamine were dissolved in a portion of the solvent, heated and stirred to carry out a prepolymerization reaction. After the reaction was completed, the mixture was cooled to room temperature, and melamine resin, acidic catalyst and the remaining solvent were added and stirred evenly to obtain the light release force, high temperature resistant non-silicone release agent.

[0013] Preferably, the preparation method of the light release force, high temperature resistant non-silicone release agent includes the following steps: dissolving epoxy resin and octadecylamine in a portion of toluene solvent, stirring at 80-100℃ for 15-60 min to carry out a prepolymerization reaction, cooling to room temperature after the reaction is completed, adding melamine resin, acidic catalyst and the remaining toluene solvent, stirring for 15-60 min to obtain the light release force, high temperature resistant non-silicone release agent.

[0014] Preferably, the preparation method of the light release force, high temperature resistant non-silicone release agent includes the following steps: dissolving epoxy resin and octadecylamine in a portion of toluene solvent, stirring at 90°C for 30 min to carry out a prepolymerization reaction, cooling to room temperature after the reaction is completed, adding melamine resin, acidic catalyst and the remaining toluene solvent, stirring for 30 min to obtain the light release force, high temperature resistant non-silicone release agent.

[0015] Preferably, the preparation method of the light release force, high temperature resistant non-silicone release agent includes the following steps: dissolving 10g of epoxy resin and 1-3g of octadecylamine in 50g of toluene solvent, stirring at 90°C for 30min to carry out a prepolymerization reaction, cooling to room temperature after the reaction is completed, adding 2g of melamine resin, 1g of acidic catalyst and another part of toluene solvent to make the solid content of the resulting solution 10%, stirring for 30min to obtain the light release force, high temperature resistant non-silicone release agent.

[0016] In a third aspect, the present invention provides a light release force, high temperature resistant non-silicone release film, which is prepared by the following method: uniformly coating the light release force, high temperature resistant non-silicone release agent as described above onto a base film, and drying it to obtain the light release force, high temperature resistant non-silicone release film.

[0017] Preferably, the light release force, high temperature resistant non-silicone release film is prepared by the following method: the light release force, high temperature resistant non-silicone release agent as described in any one of claims 1-4 is uniformly coated on a PET base film with a coating thickness of 500 nm, and dried at 120°C for 1 min to obtain the light release force, high temperature resistant non-silicone release film.

[0018] The beneficial effects of this invention are:

[0019] This invention provides a non-silicone release agent with light release force and high temperature resistance, as well as a release film based on the release agent. The non-silicone release film provided by this invention has light peel force, good resistance to damp heat, and excellent weather resistance.

[0020] In this invention, an octadecylamine and epoxy resin undergo a ring-opening reaction at high temperature to form an octadecyl epoxy resin prepolymer. Subsequently, under strong acid catalysis, the prepolymer reacts with melamine resin via the -OH groups on the epoxy resin to cure it into a film. The release agent prepared by this invention has an epoxy resin (providing adhesion and chemical resistance), a melamine resin (providing rigidity, curability, and weather resistance), and an octadecyl group (providing flexibility and low peel strength) structure, which endows the release film with low peel strength and temperature resistance. Detailed Implementation

[0021] The present invention will be further described in detail below with reference to embodiments, so that those skilled in the art can implement it based on the description.

[0022] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0023] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples are commercially available. For examples where specific conditions are not specified, conventional conditions or conditions recommended by the manufacturer are followed. For reagents or instruments whose manufacturers are not specified, they are all commercially available products.

[0024] This invention provides a non-silicone release agent with light release force and high temperature resistance, comprising the following raw material components by mass percentage: 10%-20% epoxy resin, 5%-10% melamine resin, 1%-5% octadecylamine, 0.2%-1% acid catalyst, and 80%-95% solvent.

[0025] In a preferred embodiment, the epoxy resin is at least one of bisphenol A type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin.

[0026] In a preferred embodiment, the acidic catalyst is p-toluenesulfonic acid.

[0027] In a preferred embodiment, the solvent is toluene.

[0028] This invention also provides a method for preparing the above-mentioned lightweight, high-temperature resistant non-silicone release agent, comprising the following steps:

[0029] Epoxy resin and octadecylamine were dissolved in a portion of toluene solvent and stirred at 90°C for 30 min to carry out a prepolymerization reaction. After the reaction was completed, the mixture was cooled to room temperature, and melamine resin, acidic catalyst, and the remaining toluene solvent were added. The mixture was stirred for 30 min to obtain the light release force, high temperature resistant non-silicone release agent.

[0030] The present invention also provides a light release force, high temperature resistant non-silicone release film, which is prepared by the following method: the light release force, high temperature resistant non-silicone release agent as described above is uniformly coated on the base film, and the light release force, high temperature resistant non-silicone release film is obtained after drying.

[0031] In a preferred embodiment, the base film is a PET base film, the coating thickness is 500 nm, and the drying conditions are drying at 120°C for 1 min.

[0032] In this invention, an octadecyl epoxy resin prepolymer is formed by a ring-opening reaction between octadecylamine and epoxy resin under high temperature conditions. The reaction principle is as follows:

[0033]

[0034] Wherein, R represents an octadecyl group;

[0035] Subsequently, under strong acid catalysis, the epoxy resin reacts with the melamine resin to form a film, as shown in the following principle:

[0036]

[0037] The release agent prepared by this invention has an epoxy resin (providing adhesion and chemical resistance), melamine resin (providing rigidity, curability, and weather resistance), and octadecyl (providing flexibility and low peel force) structure, which endows the release film with low peel force and temperature resistance.

[0038] The above is the general concept of the present invention. Based on this, detailed embodiments and comparative examples are provided below to further illustrate the present invention.

[0039] Example 1

[0040] A non-silicone release agent with light release force and high temperature resistance is prepared by the following steps:

[0041] 10g of bisphenol A epoxy resin and 1g of octadecylamine were dissolved in 50g of toluene solvent. The mixture was stirred at 90°C for 30 minutes to carry out a prepolymerization reaction. After the reaction was completed, the mixture was cooled to room temperature. 2g of melamine resin, 1g of p-toluenesulfonic acid, and another portion of toluene solvent were added. The amount of toluene solvent was controlled so that the solid content of the resulting solution was 10%. The mixture was stirred for 30 minutes to obtain the light release force, high temperature resistant non-silicone release agent.

[0042] A lightweight release force, high temperature resistant non-silicone release film is prepared by the following method: the lightweight release force, high temperature resistant non-silicone release agent prepared above is uniformly coated on a PET base film with a coating thickness of 500 nm, and dried at 120°C for 1 min to obtain the lightweight release force, high temperature resistant non-silicone release film.

[0043] Example 2

[0044] A non-silicone release agent with light release force and high temperature resistance is prepared by the following steps:

[0045] 10g of bisphenol A epoxy resin and 2g of octadecylamine were dissolved in 50g of toluene solvent and stirred at 90°C for 30min to carry out a prepolymerization reaction. After the reaction was completed, the mixture was cooled to room temperature, and 2g of melamine resin, 1g of p-toluenesulfonic acid and another portion of toluene solvent were added. The amount of toluene solvent was controlled so that the solid content of the resulting solution was 10%. The mixture was stirred for 30min to obtain the light release force, high temperature resistant non-silicone release agent.

[0046] A lightweight release force, high temperature resistant non-silicone release film is prepared by the following method: the lightweight release force, high temperature resistant non-silicone release agent prepared above is uniformly coated on a PET base film with a coating thickness of 500 nm, and dried at 120°C for 1 min to obtain the lightweight release force, high temperature resistant non-silicone release film.

[0047] Example 3

[0048] A non-silicone release agent with light release force and high temperature resistance is prepared by the following steps:

[0049] 10g of bisphenol A epoxy resin and 3g of octadecylamine were dissolved in 50g of toluene solvent and stirred at 90°C for 30min to carry out a prepolymerization reaction. After the reaction was completed, the mixture was cooled to room temperature, and 2g of melamine resin, 1g of p-toluenesulfonic acid and another portion of toluene solvent were added. The amount of toluene solvent was controlled so that the solid content of the resulting solution was 10%. The mixture was stirred for 30min to obtain the light release force, high temperature resistant non-silicone release agent.

[0050] A lightweight release force, high temperature resistant non-silicone release film is prepared by the following method: the lightweight release force, high temperature resistant non-silicone release agent prepared above is uniformly coated on a PET base film with a coating thickness of 500 nm, and dried at 120°C for 1 min to obtain the lightweight release force, high temperature resistant non-silicone release film.

[0051] Example 4

[0052] A non-silicone release agent with light release force and high temperature resistance is prepared by the following steps:

[0053] 10g of bisphenol F epoxy resin and 2g of octadecylamine were dissolved in 50g of toluene solvent and stirred at 90°C for 30min to carry out a prepolymerization reaction. After the reaction was completed, the mixture was cooled to room temperature, and 2g of melamine resin, 1g of p-toluenesulfonic acid and another portion of toluene solvent were added. The amount of toluene solvent was controlled so that the solid content of the resulting solution was 10%. The mixture was stirred for 30min to obtain the light release force, high temperature resistant non-silicone release agent.

[0054] A lightweight release force, high temperature resistant non-silicone release film is prepared by the following method: the lightweight release force, high temperature resistant non-silicone release agent prepared above is uniformly coated on a PET base film with a coating thickness of 500 nm, and dried at 120°C for 1 min to obtain the lightweight release force, high temperature resistant non-silicone release film.

[0055] Example 5

[0056] A non-silicone release agent with light release force and high temperature resistance is prepared by the following steps:

[0057] 10g of bisphenol S-type epoxy resin and 2g of octadecylamine were dissolved in 50g of toluene solvent. The mixture was stirred at 90°C for 30min to carry out a prepolymerization reaction. After the reaction was completed, the mixture was cooled to room temperature. Then, 2g of melamine resin, 1g of p-toluenesulfonic acid, and another portion of toluene solvent were added. The amount of toluene solvent was controlled so that the solid content of the resulting solution was 10%. The mixture was stirred for 30min to obtain the light release force, high temperature resistant non-silicone release agent.

[0058] A lightweight release force, high temperature resistant non-silicone release film is prepared by the following method: the lightweight release force, high temperature resistant non-silicone release agent prepared above is uniformly coated on a PET base film with a coating thickness of 500 nm, and dried at 120°C for 1 min to obtain the lightweight release force, high temperature resistant non-silicone release film.

[0059] Comparative Example 1

[0060] A non-silicone release agent with light release force and high temperature resistance is prepared by the following steps:

[0061] 10g of bisphenol A epoxy resin was dissolved in 50g of toluene solvent and stirred at 90°C for 30 minutes. Then, 2g of melamine resin, 1g of p-toluenesulfonic acid and another portion of toluene solvent were added. The amount of toluene solvent was controlled so that the solid content of the resulting solution was 10%. The mixture was stirred for 30 minutes to obtain the light release force, high temperature resistant non-silicone release agent.

[0062] A lightweight release force, high temperature resistant non-silicone release film is prepared by the following method: the lightweight release force, high temperature resistant non-silicone release agent prepared above is uniformly coated on a PET base film with a coating thickness of 500 nm, and dried at 120°C for 1 min to obtain the lightweight release force, high temperature resistant non-silicone release film.

[0063] Comparative Example 2

[0064] A non-silicone release agent with light release force and high temperature resistance is prepared by the following steps:

[0065] 10g of bisphenol S-type epoxy resin and 2g of triethylamine were dissolved in 50g of toluene solvent. The mixture was stirred at 90°C for 30 minutes to carry out a prepolymerization reaction. After cooling to room temperature, 2g of melamine resin, 1g of p-toluenesulfonic acid, and another portion of toluene solvent were added. The amount of toluene solvent was controlled so that the solid content of the resulting solution was 10%. The mixture was stirred for 30 minutes to obtain the light release force, high temperature resistant non-silicone release agent.

[0066] A lightweight release force, high temperature resistant non-silicone release film is prepared by the following method: the lightweight release force, high temperature resistant non-silicone release agent prepared above is uniformly coated on a PET base film with a coating thickness of 500 nm, and dried at 120°C for 1 min to obtain the lightweight release force, high temperature resistant non-silicone release film.

[0067] The release agents and release films prepared in Examples 1-5 and Comparative Examples 1-2 were subjected to the following performance tests:

[0068] 20min, 24H test method: Apply standard Nitto 31B tape to the release surface and roll it back and forth twice with a 2kg roller (300mm / min). Then place it at room temperature (23±2℃, relative humidity 50%) for 20min and 24H. Then use a universal tensile testing machine to peel it 180° at 300mm / min. Test 3 times and take the average value as the 20min and 24H release force.

[0069] 20H aging release force test method: Apply standard Nitto 31B tape to the release surface, roll it back and forth twice with a 2kg roller (300mm / min), then place it in a 55℃ oven for aging for 20H, take it out and let it sit at room temperature for 2H, and then use a universal tensile testing machine to peel it 180° at 300mm / min. Test 3 times and take the average value.

[0070] Residual testing method: Apply standard Nitto 31B tape to the release surface and roll it back and forth twice with a 2kg roller (300mm / min). Then place it in a 55℃ oven for 20 hours of aging. After aging, remove it and let it sit at room temperature for 2 hours. Peel off the Nitto 31B tape from the test sample and apply it to a standard steel plate. Roll it back and forth twice with a 2kg roller. After standing for 20 minutes, test the peel strength and record it as A1. Apply standard Nitto 31B tape to the release standard steel plate and roll it back and forth twice with a 2kg roller (300mm / min). After standing for 20 minutes, test the peel strength and record it as A2.

[0071] Residual SA% = (A1 / A2) × 100%

[0072] Release force test: Place the release film in an oven at 85℃ and 85% relative humidity for 72 hours, then remove the release film. Measure the release force after 20 minutes, 24 hours, and 20 hours of aging using the method described above.

[0073] The test results are shown in Table 1 below:

[0074] Table 1

[0075]

[0076] Comparing the mechanical property test results of Examples 1-5 and Comparative Examples 1-2 in the table, it can be seen that by using octadecylamine ring-opening epoxy resin and amino resin as a curing agent, the release film's resistance to humid heat can be improved while maintaining a low peel force. Comparative Example 1 does not contain octadecylamine, and the epoxy resin did not undergo a ring-opening reaction; therefore, no curing reaction occurred in subsequent reactions. In Comparative Example 2, octadecylamine was replaced with triethylamine, but due to the shorter alkyl chain, it did not achieve a good peeling effect in subsequent tape peeling.

[0077] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details.

Claims

1. A non-silicone release agent with light release force and high temperature resistance, characterized in that, It includes the following raw material components by mass percentage: 10%-20% epoxy resin, 5%-10% melamine resin, 1%-5% octadecylamine, 0.2%-1% acid catalyst, and 80%-95% solvent; The epoxy resin is at least one of bisphenol A type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin; The preparation method of the light release force and high temperature resistant non-silicone release agent includes the following steps: Epoxy resin and octadecylamine were dissolved in a portion of the solvent, heated and stirred to carry out a prepolymerization reaction. After the reaction was completed, the mixture was cooled to room temperature, and melamine resin, acidic catalyst and the remaining solvent were added and stirred evenly to obtain the light release force, high temperature resistant non-silicone release agent.

2. The non-silicone release agent with light release force and high temperature resistance according to claim 1, characterized in that, The acidic catalyst is p-toluenesulfonic acid.

3. The non-silicone release agent with light release force and high temperature resistance according to claim 1, characterized in that, The solvent is toluene.

4. The non-silicone release agent with light release force and high temperature resistance according to claim 1, characterized in that, The preparation method of the light release force and high temperature resistant non-silicone release agent includes the following steps: dissolving epoxy resin and octadecylamine in a portion of toluene solvent, stirring at 80-100℃ for 15-60 min to carry out a prepolymerization reaction, cooling to room temperature after the reaction is completed, adding melamine resin, acidic catalyst and the remaining toluene solvent, stirring for 15-60 min to obtain the light release force and high temperature resistant non-silicone release agent.

5. The non-silicone release agent with light release force and high temperature resistance according to claim 4, characterized in that, The preparation method of the light release force and high temperature resistant non-silicone release agent includes the following steps: dissolving epoxy resin and octadecylamine in a portion of toluene solvent, stirring at 90°C for 30 min to carry out a prepolymerization reaction, cooling to room temperature after the reaction is completed, adding melamine resin, acid catalyst and the remaining toluene solvent, stirring for 30 min to obtain the light release force and high temperature resistant non-silicone release agent.

6. The non-silicone release agent with light release force and high temperature resistance according to claim 5, characterized in that, The preparation method of the light release force and high temperature resistant non-silicone release agent includes the following steps: dissolving 10g of epoxy resin and 1-3g of octadecylamine in 50g of toluene solvent, stirring at 90°C for 30min to carry out a prepolymerization reaction, cooling to room temperature after the reaction is completed, adding 2g of melamine resin, 1g of acid catalyst and another part of toluene solvent to make the solid content of the resulting solution 10%, stirring for 30min to obtain the light release force and high temperature resistant non-silicone release agent.

7. A non-silicone release film with low release force and high temperature resistance, characterized in that, It is prepared by the following method: the light release force and high temperature resistant non-silicone release agent as described in any one of claims 1-6 is uniformly coated on the base film, and the light release force and high temperature resistant non-silicone release film is obtained after drying.

8. The non-silicone release film with light release force and high temperature resistance according to claim 7, characterized in that, It is prepared by the following method: the light release force and high temperature resistant non-silicone release agent as described in any one of claims 1-6 is uniformly coated on a PET base film with a coating thickness of 500 nm and dried at 120°C for 1 min to obtain the light release force and high temperature resistant non-silicone release film.

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