High-temperature-resistant high-stability release film and preparation method thereof

Abstract

The invention provides a high-temperature-resistant high-stability release film and a preparation method thereof. The high-temperature-resistant and high-stability release film comprises a base material layer and a release layer, the release layer is arranged on the base material layer, the release layer is formed by coating a release agent, and the raw materials of the release agent comprise modified silicon dioxide, acrylate, an acrylic monomer, soluble zinc salt and ammonia water; the modified silicon dioxide is a product obtained after hydroxylated silicon dioxide reacts with gluconic acid, and a large number of hydroxyl groups are introduced into the product. The preparation method comprises the following steps: reacting soluble zinc salt with ammonia water to form a metal complex, polymerizing acrylate and an acrylic monomer in a system to form an acrylic polymer containing more carboxyl groups, blending the acrylic polymer with other components to obtain a release agent, coating the release agent on a base material layer, and curing to obtain the high-temperature-resistant and high-stability release film. The high-temperature-resistant high-stability release film disclosed by the invention is good in stability, high in resin integration degree, and good in high temperature resistance, acid and alkali resistance and solvent resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of release films, and in particular to a high-temperature resistant and highly stable release film and a preparation method thereof. Background Art

[0002] In the field of modern material processing and industrial production, the manufacturing process of various composite materials, electronic components and packaging products often requires the use of films with specific surface properties to achieve temporary isolation or convenient peeling between materials. Release film is a key material to meet such needs. Its performance directly affects the processing efficiency and quality stability of downstream products. It has become an indispensable and important auxiliary material in industrial production.

[0003] Currently, release films are typically manufactured using polymer films as substrates. A functional coating is formed by coating the surface with a release agent and curing it. Common release agents include silicone resins and acrylate copolymers. During the preparation process, adjustments to the formulation ratios and different curing processes are often required to control the release film's basic properties, such as peel strength and surface smoothness, to meet the needs of different applications.

[0004] However, existing release films still have numerous performance limitations, making it difficult to meet growing industrial demands. For example, some products are prone to substrate shrinkage or coating cracking at high temperatures, resulting in wrinkling and deformation of the film surface. Some release films lack acid and alkali resistance, which can lead to performance degradation under acidic and alkaline conditions. Furthermore, when exposed to organic solvents or water, the coatings swell and dissolve easily, resulting in low weight retention, which affects their stable application under complex working conditions.

[0005] In summary, a new technical solution is urgently needed to solve the problems existing in the existing technology. Summary of the Invention

[0006] Based on this, the present invention provides a high-temperature resistant and highly stable release film and a preparation method thereof. The high-temperature resistant and highly stable release film comprises a substrate layer and a release layer, wherein the release layer is arranged on the substrate layer, and the release layer is formed by coating a release agent. The raw materials of the release agent include modified silica, acrylate, acrylic acid monomer, soluble zinc salt and ammonia water; the modified silica is the product of the reaction of hydroxylated silica and gluconic acid, and a large number of hydroxyl groups are introduced. The present invention first reacts the soluble zinc salt with ammonia water to form a metal complex (the whole system is alkaline at this time), and then polymerizes the acrylate and acrylic acid monomer in the system to form an acrylic polymer with more carboxyl groups, and blends it with an organosilicon resin, a hydrogenated silicone oil, modified silica and a platinum catalyst to form a release agent, which is coated on the substrate layer and cured to obtain a high-temperature resistant and highly stable release film. During the curing process, due to the volatilization of ammonia water at high temperature, the pH of the system decreases (the carboxyl groups in the system are gradually protonated to form carboxylic acids), and Zn 2+ It is released and chelates with the hydroxyl groups on the modified silica and the carboxylic acid on the acrylic polymer to form a chelate, thereby stabilizing the entire system and improving the degree of resin integration, thereby improving the high temperature resistance, acid and alkali resistance, and solvent resistance of the release film.

[0007] One object of the present invention is to provide a high-temperature resistant and highly stable release film, comprising a substrate layer and a release layer, wherein the release layer is disposed on the substrate layer and is formed by coating a release agent, wherein the raw materials of the release agent include the following components in parts by mass:

[0008]

[0009] in,

[0010] The modified silicon dioxide is a product of the reaction between hydroxylated silicon dioxide and gluconic acid.

[0011] Furthermore, the material of the substrate layer is polyethylene (PE) or polyethylene terephthalate (PET).

[0012] Furthermore, the soluble zinc salt is zinc chloride (ZnCl2).

[0013] Furthermore, the initiator is selected from one or more of ammonium persulfate or sodium persulfate.

[0014] Furthermore, the emulsifier is selected from one or more of isomeric decanol polyoxyethylene ether, nonylphenol allyl polyoxyethylene ether ammonium sulfate or polyoxyethylene alkyl ether.

[0015] Furthermore, the mass concentration of the ammonia water is 10-25wt%.

[0016] Another object of the present invention is to provide a method for preparing the above-mentioned high-temperature resistant and highly stable release film, comprising the following steps:

[0017] S1, mixing hydroxylated silicon dioxide and gluconic acid, heating and reacting to obtain modified silicon dioxide;

[0018] S2, dissolving a soluble zinc salt in part of the water to obtain a zinc salt solution; uniformly mixing aqueous ammonia, an emulsifier, and the remaining water, adding the zinc salt solution, heating and stirring to react, then adding acrylate, methyl acrylate, methyl methacrylate, and an initiator, continuing the heating reaction to obtain an intermediate product;

[0019] S3. Evenly blending the intermediate product, silicone resin, hydrogenated silicone oil, modified silicon dioxide and platinum catalyst to obtain a release agent; coating the release agent on a substrate layer, and curing the release agent to obtain a high-temperature resistant and highly stable release film.

[0020] Furthermore, in step S1, the mass ratio of the hydroxylated silicon dioxide to gluconic acid is 1:(1-5).

[0021] Furthermore, in step S1, the heating temperature is 60-80°C.

[0022] Furthermore, in step S2, the heating temperature is 60-80°C.

[0023] The present invention has the following beneficial effects:

[0024] The present invention provides a high-temperature resistant and highly stable release film and a preparation method thereof. The high-temperature resistant and highly stable release film comprises a substrate layer and a release layer, wherein the release layer is arranged on the substrate layer, and the release layer is formed by coating a release agent. The raw materials of the release agent include modified silica, acrylate, acrylic acid monomer, soluble zinc salt and ammonia water; the modified silica is the product of the reaction of hydroxylated silica and gluconic acid, and a large number of hydroxyl groups are introduced. The present invention first reacts the soluble zinc salt and ammonia water to form a metal complex (the entire system is alkaline at this time), and then polymerizes the acrylate and acrylic acid monomer in the system to form an acrylic polymer with more carboxyl groups, and blends it with an organosilicon resin, hydrogenated silicone oil, modified silica and a platinum catalyst to form a release agent, which is coated on the substrate layer and cured to obtain a high-temperature resistant and highly stable release film. During the curing process, due to the volatilization of ammonia water at high temperature, the pH of the system decreases (the carboxyl groups in the system are gradually protonated to form carboxylic acids), and Zn 2+ It is released and chelates with the hydroxyl groups on the modified silica and the carboxylic acid on the acrylic polymer to form a chelate, thereby stabilizing the entire system and improving the degree of resin integration, thereby improving the high temperature resistance, acid and alkali resistance, and solvent resistance of the release film. DETAILED DESCRIPTION

[0025] In order to more clearly illustrate the technical solutions of the present invention, the following examples are given. Unless otherwise stated, the raw materials, reactions and post-processing methods mentioned in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0026] The terms "preferred," "preferably," "more preferred," and the like, used herein, refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

[0027] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties to be obtained by the present invention.

[0028] The present invention uses the following raw materials:

[0029] Organic silicone resin: methyl vinyl MQ silicone resin, vinyl content (mass ratio) is 0.8%, purchased from Shanghai Puzhen Biotechnology Co., Ltd. (Kramer).

[0030] Ammonia water: concentration is 25wt%.

[0031] Emulsifier: isomeric decanol polyoxyethylene ether.

[0032] Hydrogen-containing silicone oil: hydrogen content (%, m / m) ≥ 1.55, purchased from Jiangxi Haiduo Chemical Co., Ltd.

[0033] The preparation method of hydroxylated silicon dioxide comprises the following steps:

[0034] The silica was immersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide (concentrated sulfuric acid: hydrogen peroxide = 7:3, m / m, the concentration of the hydrogen peroxide was 30 wt%), reacted at 80° C. for 1 h, and the unreacted concentrated sulfuric acid and hydrogen peroxide were washed away to obtain hydroxylated silica.

[0035] The water in the present invention is all deionized water.

[0036] The "parts" in the present invention refer to parts by mass.

[0037] Example 1

[0038] A high-temperature resistant and highly stable release film comprises a substrate layer and a release layer, wherein the release layer is provided on the substrate layer and is formed by coating a release agent, wherein the raw materials of the release agent include the following components in parts by mass:

[0039]

[0040] in,

[0041] The modified silicon dioxide is a product of the reaction between hydroxylated silicon dioxide and gluconic acid;

[0042] The substrate layer is a PET film with a thickness of 50 μm.

[0043] The method for preparing the high-temperature resistant and highly stable release film comprises the following steps:

[0044] S1. Using DMF (N,N-dimethylformamide) as a solvent, hydroxylated silica and gluconic acid were mixed (hydroxylated silica:gluconic acid mixture = 1:3, m / m), reacted at 70° C. for 80 h, filtered, washed, and dried to obtain modified silica;

[0045] S2. Dissolve zinc chloride with 1 part of water according to the above-mentioned mass fractions to obtain a zinc salt solution; evenly mix aqueous ammonia, an emulsifier, and the remaining water, then add the zinc salt solution, stir and react at 80° C. for 15 minutes, then add sodium acrylate, methyl acrylate, methyl methacrylate, and ammonium persulfate, continue heating and reacting for 2 hours, and cool after the reaction is completed to obtain an intermediate product;

[0046] S3. Evenly blend the intermediate product, silicone resin, hydrogenated silicone oil, modified silicon dioxide and platinum catalyst to obtain a release agent; apply the release agent on the PET substrate layer with a thickness of 0.1 μm, and cure at 130° C. for 4 minutes to obtain a high-temperature resistant and highly stable release film.

[0047] Example 2

[0048] A high-temperature resistant and highly stable release film comprises a substrate layer and a release layer, wherein the release layer is provided on the substrate layer and is formed by coating a release agent, wherein the raw materials of the release agent include the following components in parts by mass:

[0049]

[0050] in,

[0051] The modified silicon dioxide is a product of the reaction between hydroxylated silicon dioxide and gluconic acid;

[0052] The substrate layer is a PET film with a thickness of 50 μm.

[0053] The preparation method of the high temperature resistant and highly stable release film is the same as that of Example 1.

[0054] Example 3

[0055] A high-temperature resistant and highly stable release film comprises a substrate layer and a release layer, wherein the release layer is provided on the substrate layer and is formed by coating a release agent, wherein the raw materials of the release agent include the following components in parts by mass:

[0056]

[0057]

[0058] in,

[0059] The modified silicon dioxide is a product of the reaction between hydroxylated silicon dioxide and gluconic acid;

[0060] The substrate layer is a PET film with a thickness of 50 μm.

[0061] The preparation method of the high temperature resistant and highly stable release film is the same as that of Example 1.

[0062] Comparative Example 1

[0063] A high-temperature resistant and highly stable release film. The difference between this comparative example and Example 1 is that zinc chloride is not added, and the other steps and amounts are the same as those in Example 1.

[0064] Comparative Example 2

[0065] A high-temperature resistant and highly stable release film. The difference between this comparative example and Example 1 is that step S1 is not performed, and in step S3, the modified silica is replaced by unmodified silica. The other steps and amounts are the same as those in Example 1.

[0066] Test Case

[0067] The performance of the high temperature resistant and highly stable release films of Examples 1-3 and Comparative Examples 1-2 was tested.

[0068] Test method:

[0069] (1) High temperature resistance: Place the high temperature resistant and highly stable release film at 200°C for 20 minutes and observe whether it wrinkles.

[0070] (2) Acid and alkali resistance: The high temperature resistant and high stability release film was immersed in 0.1M hydrochloric acid solution and 0.1M sodium hydroxide solution for 12 hours respectively, then taken out and washed with deionized water to observe the changes in appearance.

[0071] (3) Solvent resistance: The silicon-coated release film to be tested was immersed in toluene, acetone, ethanol, and water for 108 hours, then taken out, dried, and weighed to calculate the weight retention rate.

[0072] Weight retention (%) = (W2 / W1) x 100%.

[0073] W1 is the mass before immersion, g; W2 is the mass after immersion, g.

[0074] The test results are shown in Table 1.

[0075] Table 1 Release film performance test results

[0076]

[0077] The above test results show that the high-temperature-resistant, high-stability release film of the present invention exhibits excellent high-temperature resistance, remaining wrinkle-free after 20 minutes at 200°C. It also exhibits excellent acid and alkali resistance, showing no cracking or discoloration after immersion in 0.1M hydrochloric acid solution and 0.1M sodium hydroxide solution for 12 hours. It also exhibits excellent solvent resistance, with weight retention rates exceeding 99% after immersion in toluene, acetone, ethanol, and water for 108 hours. Comparative Example 1 does not add zinc chloride, and Comparative Example 2 replaces the modified silica with unmodified silica. The degree of component integration in both cases is inferior to that of the present invention, resulting in inferior high-temperature resistance, acid and alkali resistance, and solvent resistance.

[0078] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0079] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A high temperature resistant and highly stable release film, comprising a substrate layer and a release layer, characterized in that: The release layer is provided on the substrate layer, and the release layer is formed by coating a release agent. The raw materials of the release agent include the following components in parts by mass: in, The modified silicon dioxide is a product of the reaction between hydroxylated silicon dioxide and gluconic acid.

2. The high temperature resistant and highly stable release film according to claim 1, characterized in that: The soluble zinc salt is zinc chloride.

3. The high temperature resistant and highly stable release film according to claim 1, characterized in that: The initiator is selected from one or more of ammonium persulfate and sodium persulfate.

4. The high temperature resistant and highly stable release film according to claim 1, characterized in that: The emulsifier is selected from one or more of isomeric decanol polyoxyethylene ether, nonylphenol allyl polyoxyethylene ether ammonium sulfate or polyoxyethylene alkyl ether.

5. The high temperature resistant and highly stable release film according to claim 1, characterized in that: The mass concentration of the ammonia water is 10-25 wt%.

6. The method for preparing the high temperature resistant and highly stable release film according to any one of claims 1 to 5, characterized in that: The steps include: S1, mixing hydroxylated silicon dioxide and gluconic acid, heating and reacting to obtain modified silicon dioxide; S2, dissolving a soluble zinc salt in part of the water to obtain a zinc salt solution; uniformly mixing aqueous ammonia, an emulsifier, and the remaining water, adding the zinc salt solution, heating and stirring to react, then adding acrylate, methyl acrylate, methyl methacrylate, and an initiator, continuing the heating reaction to obtain an intermediate product; S3. Evenly blending the intermediate product, silicone resin, hydrogenated silicone oil, modified silicon dioxide and platinum catalyst to obtain a release agent; coating the release agent on a substrate layer, and curing the release agent to obtain a high-temperature resistant and highly stable release film.

7. The method for preparing a high-temperature resistant and highly stable release film according to claim 6, wherein: In step S1, the mass ratio of the hydroxylated silicon dioxide to gluconic acid is 1:(1-5).

8. The method for preparing a high-temperature resistant and highly stable release film according to claim 6, wherein: In step S1, the heating temperature is 60-80°C.

9. The method for preparing a high-temperature resistant and highly stable release film according to claim 6, wherein: In step S2, the heating temperature is 60-80°C.

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