A kind of organosilicon heavy release regulator and its preparation and application

Abstract

The present invention relates to the technical field of silicone release agents, and in particular to a method for preparing and applying a heavy-peeling force regulator for silicone release agents. The present invention provides a silicone heavy-peeling force regulator, the components of which include: 60 to 80 parts by weight of a modified vinyl MQ resin, 10 to 30 parts by weight of a diluent, 1 to 2 parts by weight of an inhibitor, and 5 to 10 parts by weight of a vinyl polysiloxane; wherein the inhibitor is an alkynol oligomer; the modified vinyl MQ resin is prepared by the following method: adding hexamethyldisilazane and an alcohol substance to a vinyl MQ resin, and performing a hydrolysis condensation reaction at 40 to 60°C to obtain the modified vinyl MQ resin. The present invention uses a self-synthesized modified vinyl MQ resin to control the configuration of the MQ resin, thereby improving the release force stability of the release agent after adding the heavy-peeling force regulator and maintaining a high residual adhesion rate; the release force of the resulting release protective film has a low aging increase.

Description

Technical Field

[0001] The present invention relates to the technical field of organosilicon release agents, and in particular to a preparation and application method of a heavy-stripping regulator for organosilicon release agents. Background Art

[0002] Silicone release agents offer advantages such as excellent transparency, stability, high and low temperature resistance, and adjustable release force. When coated onto film substrates such as PET, PE, and PI, they can be used to create release films, which are widely used in the functional film, touchscreen, and electronics industries. These industries each have varying requirements for release force, and silicone release agents are relatively scarce. Consequently, release modifiers for silicone release agents have emerged.

[0003] A release modifier is a release force adjustment aid for silicone release agents, and the release force of silicone release agents can be adjusted through the release modifier. Release modifiers are divided into heavy release modifiers (to increase the release force of the release agent) and light release modifiers (to reduce the release force of the release agent). The main component of the heavy release modifier is MQ resin with a larger molecular configuration, and its normal form is powder. For ease of use, heavy release modifiers on the market are mainly prepared by dissolving MQ resin in toluene or other volatile solvents to form MQ resin solutions, but toluene or volatile solvents are volatile and toxic. In recent years, the country's requirements for the management of solvents and toxic and hazardous substances have become increasingly stringent, and the use of products containing toluene or other volatile substances has become increasingly restricted. In addition, the addition of heavy release modifiers will cause the release force of the release agent to increase significantly after aging, which may be restricted during application.

[0004] Patent CN202110263906.2 discloses a method for synthesizing a solvent-free heavy-stripping regulator for silicone release. The invention provides a method for synthesizing a solvent-free heavy-stripping regulator for silicone release and its application, comprising the following steps: S1, taking MQ silicone resin and vinyl mono-terminated silicone oil in a solvent and stirring evenly; S2, adding a catalyst, stirring and reacting at 50-100°C for 5-8 hours; S3, adding silane to the system obtained in S2, stirring and reacting at 50-75°C for 3-5 hours; S4, washing the system obtained in S3 with deionized water 3-5 times, and separating the water layer; S5, adding low-viscosity vinyl-terminated silicone oil to the system obtained in S4, removing low-boiling substances under reduced pressure, and obtaining a heavy-stripping regulator. However, when the addition amount of the heavy release regulator prepared by this method is 30%, the measured release force is 18.6-21.3g / 25mm, and the aging climbing rate is 180%-187%. There are problems such as a narrow adjustment range of the release force and a large aging climbing rate of the release force. Summary of the Invention

[0005] To address the above-mentioned drawbacks, the present invention utilizes a specific vinyl MQ resin, a diluent, an acetylene alcohol oligomer inhibitor, and vinyl polysiloxane as raw materials to produce a novel release modifier for silicone release agents. In the present invention, by controlling the vinyl content during the synthesis of the specific vinyl MQ resin and employing a hexamethyldisilazane treatment process, the modified vinyl MQ resin obtained can improve the release force stability of the release agent after the addition of the heavy release modifier, maintaining a high residual adhesion rate. Furthermore, the use of long-chain olefins (such as C 12 ~C 20 The use of a mixture of alkynol oligomers as an inhibitor ensures that the addition of different amounts of heavy release agent does not affect the release agent's curing speed. This also ensures that the release agent's curing speed and operating time are not affected when the heavy release agent is added in high amounts or is used alone. Furthermore, the addition of a low-viscosity vinyl polysiloxane ensures that the heavy release agent has better coating and film-forming properties during use. This also ensures that the coated release protective film will not suffer from powdering or debonding when the heavy release agent is added in high amounts to the release agent or is used alone.

[0006] The technical solution of the present invention:

[0007] The first technical problem to be solved by the present invention is to provide an organosilicon heavy release regulator, the components of which include: 60 to 80 parts by weight of a modified vinyl MQ resin, 10 to 30 parts by weight of a diluent, 1 to 2 parts by weight of an inhibitor, and 5 to 10 parts by weight of a vinyl polysiloxane; wherein the inhibitor is an acetylene alcohol oligomer;

[0008] The modified vinyl MQ resin is prepared by the following method: adding hexamethyldisilazane and alcohol substances into a solution of vinyl MQ resin, and performing hydrolysis condensation reaction at 40-60° C. to prepare the modified vinyl MQ resin.

[0009] Furthermore, the modified vinyl MQ resin has a vinyl content of 0.3 to 2%, preferably 0.5 to 1.2%.

[0010] Furthermore, the weight average molecular weight of the modified vinyl MQ resin is 3000 to 8000, preferably 4000 to 6000.

[0011] Furthermore, the acetylene alcohol oligomer is selected from at least one of acetylene alcohol oligomer, butynol oligomer, ethynylcyclohexanol oligomer or hexynol oligomer; the use of acetylene alcohol oligomer can have a better room temperature inhibition effect and can achieve rapid curing under heating conditions.

[0012] Furthermore, the diluent is a long-chain olefin, preferably C12 ~C 20 At least one of the olefins.

[0013] Furthermore, the vinyl polysiloxane is a terminal vinyl polysiloxane.

[0014] Furthermore, the molecular structure of the terminal vinyl polysiloxane is

[0015] Wherein: Vi is vinyl, R is vinyl or methyl, x, y, z are all natural numbers, 0≤x≤5, 1≤y≤4, 0≤z≤5.

[0016] Furthermore, the vinyl content of the vinyl polysiloxane is 0.5 to 1.5%.

[0017] Furthermore, the viscosity of the vinyl polysiloxane is 500 to 50,000 mPa·s.

[0018] Furthermore, the modified vinyl MQ resin is prepared by a method comprising: preparing 100 parts of a vinyl MQ resin using conventional techniques, adding 25-50 parts of toluene, and stirring to dissolve; after the resin is completely dissolved, adding 1-4 parts of hexamethyldisilazane, 0.5-2 parts of an alcohol, and 0.5-2 parts of distilled water; heating the mixture to 40-60°C, and hydrolyzing and condensing the mixture for 2-3 hours; and finally heating the hydrolyzed and condensed resin to 100-110°C and distilling the mixture to obtain the modified vinyl MQ resin. In the present invention, the vinyl MQ resin prepared using conventional techniques is a publicly available material and can be obtained from any source, either purchased or homemade.

[0019] Furthermore, the alcohol substance is at least one of isopropyl alcohol, methanol, ethylene glycol, glycerol or n-butanol.

[0020] The second technical problem to be solved by the present invention is to provide a preparation method of the above-mentioned silicone heavy release regulator, which comprises the following steps: (1) adding the modified vinyl MQ resin into a reactor; (2) adding a diluent and stirring evenly; (3) adding vinyl polysiloxane and stirring evenly; (4) adding an inhibitor and stirring evenly.

[0021] The third technical problem to be solved by the present invention is to point out that the above-mentioned organosilicon heavy release regulator can be used as an auxiliary agent of organosilicon release agent, and can also be used as a release agent alone.

[0022] The heavy release regulator in the present invention can be used not only in combination with a silicone release agent, but can also be used alone. When used alone, the release force of the release protective film produced can reach 1000g / 25mm. At the same time, it does not contain volatile solvents and can be widely used in the field of release protective films in functional films, touch screen industries and electronics industries.

[0023] The fourth technical problem to be solved by the present invention is to provide a method for preparing a release protective film, the preparation method comprising the following steps:

[0024] 1) Preparation of release agent glue solution: 100 parts of the above-prepared heavy release agent and 0-300 parts of release agent are mixed and stirred uniformly; based on the total weight of the heavy release agent and release agent, 2.5-10 parts of cross-linking agent are added under slow stirring and stirred for 2-10 minutes; then 1.5-6 parts of anchoring agent are added and stirred for 2-10 minutes; finally, 1.5-6 parts of catalyst are added and stirred for 10-30 minutes to prepare glue solution;

[0025] 2) Release agent glue coating and curing: first evenly apply the glue on the substrate, and then cure the substrate coated with the glue at 90-120°C for 10-30 seconds to obtain the release protective film.

[0026] Furthermore, the release agent is DOW-9106, the cross-linking agent is DOW-7028, the anchoring agent is DOW-9176, and the catalyst is DC-4000, all of which are commercially available products of DOW.

[0027] Furthermore, the substrate is PET film, PE film, PEK coated paper or glassine paper.

[0028] The fifth technical problem to be solved by the present invention is to provide a release protective film, which is prepared by the above method.

[0029] Furthermore, the dry silicon content of the release protective film is 0.1 to 2 g / m 2 .

[0030] Furthermore, when the heavy release regulator and the silicone release agent are used in combination, when the addition amount of the heavy release regulator is 5 to 90%, the initial release force of the resulting release protective film is 30 to 800 g / 25 mm, the release force aging increase at 70°C is less than 30%, and the residual adhesion rate after aging at 70°C is ≥90%.

[0031] Furthermore, when the heavy release agent is used alone, the initial release force of the resulting release protective film is ≥1000 g / 25 mm, the release force rises by less than 50% after aging at 70° C., and the residual adhesion rate after aging at 70° C. is ≥50%.

[0032] The sixth technical problem to be solved by the present invention is to provide a preparation method of a modified vinyl MQ resin, wherein the preparation method comprises adding hexamethyldisilazane and an alcohol substance to a vinyl MQ resin solution, hydrolyzing and condensing the solution at 40 to 60° C., and then distilling the solution to obtain the modified vinyl MQ resin.

[0033] Furthermore, the preparation method of the modified vinyl MQ resin is as follows: 100 parts of vinyl MQ resin are prepared by existing technology, 25 to 50 parts of toluene are added, and the mixture is stirred and dissolved; after the resin is completely dissolved, 1 to 4 parts of hexamethyldisilazane, 0.5 to 2 parts of alcohol substances, and 0.5 to 2 parts of distilled water are added, the mixture is heated to 50 to 60° C., and hydrolyzed and condensed for 2 to 3 hours; finally, the resin after the hydrolysis and condensation is completed is heated to 100 to 110° C. and distilled to obtain the modified vinyl MQ resin.

[0034] Furthermore, the alcohol is at least one of isopropanol, methanol, ethylene glycol, glycerol or n-butanol.

[0035] Furthermore, the preparation method of the vinyl MQ resin comprises the following steps:

[0036] (1) Add concentrated hydrochloric acid, anhydrous ethanol, and distilled water to a reactor and start stirring. The weight ratio of concentrated hydrochloric acid, anhydrous ethanol, and distilled water is 1:1-1.5:1-2;

[0037] (2) adding the end-capping agent into the reactor and heating to reflux;

[0038] (3) After reflux occurs, add a mixture of sodium silicate and distilled water, raise the temperature to 45-55°C and maintain, and hydrolyze for 2.5-4 hours, wherein the weight ratio of sodium silicate to the blocking agent is 1:0.3-0.5, the weight ratio of sodium silicate to distilled water is 1:1.5-2.5, and the weight ratio of sodium silicate to concentrated hydrochloric acid is 1:1-1.5;

[0039] (4) adding hexamethyldisiloxane, raising the temperature to 55-70° C., and maintaining the temperature for 1-2 hours, wherein the weight ratio of sodium silicate to hexamethyldisiloxane is 1:2-3;

[0040] (5) Allow to cool and separate, take the supernatant and wash with distilled water, then continue to allow to separate, repeat 2-4 times;

[0041] (6) Take the supernatant liquid, heat it to 100-110°C and distill it to obtain vinyl MQ resin.

[0042] Furthermore, in the preparation method of the vinyl MQ resin, the end-capping agent is a mixture of one or more of hexamethyldisiloxane, trimethylalkoxysilane, dimethylvinylalkoxysilane, vinyl double end-capping agent or vinyl single end-capping agent.

[0043] Furthermore, in the preparation method of the vinyl MQ resin, the modulus of the sodium silicate is 1.5 to 3.5, and the silicon dioxide content is 25% to 30%.

[0044] The seventh technical problem to be solved by the present invention is to provide a modified vinyl MQ resin, which is prepared by the above preparation method.

[0045] Furthermore, the modified vinyl MQ resin has a vinyl content of 0.3 to 2%, preferably 0.5 to 1.2%.

[0046] Furthermore, the weight average molecular weight of the modified vinyl MQ resin is 3000 to 8000, preferably 4000 to 6000.

[0047] The eighth technical problem to be solved by the present invention is to point out that the above-mentioned modified vinyl MQ resin is used to prepare a silicone heavy-release regulator, that is, the silicone heavy-release regulator is prepared using modified vinyl MQ resin, inhibitor, diluent and vinyl polysiloxane as raw materials; wherein the proportion of each component is: 60 to 80 parts by weight of modified vinyl MQ resin, 10 to 30 parts by weight of diluent, 1 to 2 parts by weight of inhibitor and 5 to 10 parts by weight of vinyl polysiloxane; wherein the inhibitor is an acetylene alcohol oligomer.

[0048] In the present invention, unless otherwise specified, parts are by weight.

[0049] Compared with existing commercially available heavy peeling regulators, the present invention has the following beneficial effects:

[0050] 1. The heavy-stripping regulator prepared by the present invention is a solvent-free system, which uses long-chain olefins to dissolve the resin. The long-chain olefins can react with the cross-linking agent, thus solving the problems of solvent volatilization, pollution and toxicity.

[0051] 2. The present invention adopts a self-synthesized modified vinyl MQ resin. By controlling the vinyl content during the synthesis process of the vinyl MQ resin, the vinyl MQ resin is modified with hexamethyldisilazane to control the configuration of the MQ resin, thereby improving the release force stability of the release agent after adding a heavy peel force regulator and maintaining a high residual adhesion rate. The resulting release protective film has a low aging increase in release force and a high aging residual adhesion rate.

[0052] 3. The present invention uses a mixture of multiple acetylenic alcohol oligomers as an inhibitor to increase the curing speed of the product at 90°C to 120°C, and ensures the curing speed and operation time when a high amount of heavy-stripping regulator is added.

[0053] 4. The present invention can add low-viscosity vinyl polysiloxane to make the heavy-release regulator have better coating and film-forming properties when used, while ensuring that the heavy-release regulator will not have powdering and degumming problems when used alone; and the vinyl content of the vinyl polysiloxane is controlled to be 0.5-1.5%. Too low a vinyl content will reduce the residual adhesion rate of the product, and too high a vinyl content will affect the release force adjustment efficiency.

[0054] 5. The heavy-release agent prepared by the present invention can be used not only in conjunction with a silicone release agent, but also on its own. The release force of the release film produced by using it alone can reach 1000g / 25mm, and its use alone does not affect the product curing and film formation. DETAILED DESCRIPTION

[0055] The following is a clear and complete description of the technical solution for preparing the heavy-stripping conditioning agent of the present invention, in conjunction with specific embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0056] The following examples provide a detailed description of the preparation and application of the releasable release agent of the present invention. Each example utilizes the synthesis and modification of a vinyl MQ resin, the preparation of the releasable release agent, and the preparation and testing of a release film as examples. In each example, all parts are by weight unless otherwise stated.

[0057] Example 1

[0058] To synthesize vinyl MQ resin: Add 60 parts concentrated hydrochloric acid, 60 parts anhydrous ethanol, and 60 parts distilled water to a reactor and start stirring. Weigh 21.4 parts hexamethyldisiloxane and 1.72 parts vinyl double-end cap, mix thoroughly, and add to the reactor. Set the temperature to 40°C and reflux for 30 minutes. After the liquid in the reactor has refluxed for 30 minutes, quickly add a mixture of 60 parts sodium silicate and 120 parts distilled water. Heat to 45°C and maintain hydrolysis for 3 hours. Then, add 130 parts hexamethyldisiloxane extract, set the temperature to 65°C, and extract for 1.5 hours. After extraction, allow the mixture to stand and separate. Remove the supernatant and wash it one to two times with 150 parts distilled water. Continue to let the mixture stand and separate. Remove the supernatant to obtain approximately 170 parts of resin solution. Heat the supernatant to 110°C and distill to obtain vinyl MQ resin.

[0059] Vinyl MQ Resin Modification: Place 50 parts of vinyl MQ resin in a reaction kettle, add 21 parts of toluene, and stir to dissolve. Once the resin is completely dissolved, add 1 part of hexamethyldisilazane, 0.5 parts of isopropyl alcohol, and 0.5 parts of distilled water. Heat to 60°C for hydrolysis and condensation for 3 hours. Finally, heat the resulting resin solution to 110°C and distill to obtain modified vinyl MQ resin.

[0060] Preparation of a heavy-release agent: 65 parts of the modified vinyl MQ resin prepared above were added to a reaction kettle, followed by 25 parts of tetradecene, 10 parts of a vinyl-terminated silicone oil with a viscosity of 1000 mPa·s and a vinyl content of 0.5%, and 1.5 parts of an acetylene alcohol oligomer. The mixture was stirred evenly to obtain a heavy-release agent.

[0061] Preparation of 1# release agent glue: Mix 100 parts of the prepared heavy peeling regulator and 300 parts of DOW-9106 release agent and stir evenly, add 10 parts of cross-linking agent DOW-7028 and stir for 5 minutes; then add 6 parts of anchoring agent DOW-9176 and stir for 5 minutes; finally add 6 parts of catalyst DC-4000 and stir for 30 minutes.

[0062] Preparation of 2# release agent glue: Mix 100 parts of the prepared heavy-peeling regulator and 100 parts of DOW-9106 release agent and stir evenly. Add 5 parts of DOW-7028 under slow stirring and stir for 5 minutes; then add 3 parts of DOW-9176 and stir for 5 minutes; finally add 3 parts of DC-4000 and stir for 30 minutes.

[0063] Preparation of 3# release agent glue: Take 100 parts of the prepared heavy release regulator, add 2.5 parts of DOW-7028 under slow stirring, stir for 5 minutes; then add 1.5 parts of DOW-9176, stir for 5 minutes; finally add 1.5 parts of DC-4000, stir for 30 minutes.

[0064] Release agent glue coating and curing: The prepared glue is evenly coated on the PET film, and then placed in a 120°C oven for curing for 20 seconds. After taking it out, it is promptly placed in a sealed bag to obtain a release protective film, which is respectively recorded as 1# release protective film (corresponding to 1# release agent glue), 2# release protective film (corresponding to 2# release agent glue), and 3# release protective film (corresponding to 3# release agent glue) in Example 1.

[0065] Release film testing: A dry silicon tester was used to measure the film's coating thickness. Tesa 7475 tape was used to test the film's initial and aged release force. 31B tape was used to test the film's residual adhesion after aging. Performance parameters are shown in Tables 1 and 2.

[0066] Example 2

[0067] Synthesis of vinyl MQ resin: same as in Example 1.

[0068] Vinyl MQ resin modification: same as Example 1.

[0069] Preparation of the heavy-release agent: Add 75 parts of modified vinyl MQ resin to a reactor, add 20 parts of tetradecene, then add 5 parts of end-side vinyl silicone oil with a viscosity of 700 mPa·s and a vinyl content of 0.6%, and 1.5 parts of butynol oligomer, and stir evenly to obtain the heavy-release agent.

[0070] Preparation of release agent glue: same as in Example 1.

[0071] Release agent glue coating and curing: Same as Example 1, the prepared release protective films are respectively recorded as 3# release protective film, 4# release protective film, and 5# release protective film of Example 2.

[0072] Release film testing: same as in Example 1.

[0073] Example 3

[0074] To synthesize vinyl MQ resin: Add 70 parts concentrated hydrochloric acid, 100 parts anhydrous ethanol, and 120 parts distilled water to a reactor and start stirring. Weigh 22.9 parts hexamethyldisiloxane and 4.1 parts vinyl double-end cap, mix thoroughly, and add to the reactor. Set the temperature to 40°C and reflux for 35 minutes. After the liquid in the reactor refluxes for 30 minutes, quickly add a mixture of 70 parts sodium silicate and 105 parts distilled water. Heat to 50°C and maintain hydrolysis for 3.5 hours. Then, add 150 parts hexamethyldisiloxane extract, set the temperature to 60°C, and extract for 2 hours. After extraction, allow the mixture to stand and separate. Remove the supernatant and wash it with 180 parts distilled water once or twice. Continue to allow the mixture to stand and separate. Remove the supernatant to obtain approximately 200 parts of resin solution. Heat the supernatant to 110°C and distill to obtain vinyl MQ resin.

[0075] Vinyl MQ Resin Modification: Place 50 parts of vinyl MQ resin in a reaction kettle, add 21 parts of toluene, and stir to dissolve. Once the resin is completely dissolved, add 1 part of hexamethyldisilazane, 0.5 parts of isopropyl alcohol, and 0.5 parts of distilled water. Heat to 60°C for hydrolysis and condensation for 3 hours. Finally, heat the hydrolysis and condensation-completed resin solution to 110°C and distill to obtain vinyl MQ resin.

[0076] Preparation of heavy peeling regulator: same as in Example 1.

[0077] Preparation of release agent glue: same as in Example 1.

[0078] Release agent glue coating and curing: Same as Example 1, the prepared release protective films are respectively recorded as 7# release protective film, 8# release protective film, and 9# release protective film in Example 3.

[0079] Release film testing: same as in Example 1.

[0080] Comparative Example 1

[0081] Preparation of 10# release agent glue: Mix 100 parts of CRA-17 and 300 parts of DOW-9106 release agent and stir evenly. Add 10 parts of DOW-7028 under slow stirring and stir for 5 minutes; then add 6 parts of DOW-9176 and stir for 5 minutes; finally add 6 parts of DC-4000 and stir for 30 minutes.

[0082] Preparation of 11# release agent glue: Mix 100 parts of CRA-17 and 100 parts of DOW-9106 release agent and stir evenly. Add 5 parts of DOW-7028 under slow stirring and stir for 5 minutes; then add 3 parts of DOW-9176 and stir for 5 minutes; finally add 3 parts of DC-4000 and stir for 30 minutes.

[0083] Preparation of 12# release agent glue: Take 100 parts of CRA-17, add 2.5 parts of DOW-7028 under slow stirring, stir for 5 minutes; then add 1.5 parts of DOW-9176, stir for 2 to 10 minutes; finally add 1.5 parts of DC-4000, stir for 30 minutes.

[0084] Glue coating and curing: the same as in Example 1; the prepared release protective films are respectively recorded as 10# release protective film, 11# release protective film, and 12# release protective film of Comparative Example 1.

[0085] Release film testing: same as in Example 1.

[0086] Comparative Example 2

[0087] To synthesize vinyl MQ resin: Add 60 parts concentrated hydrochloric acid, 60 parts anhydrous ethanol, and 60 parts distilled water to a reactor and start stirring. Weigh 21.4 parts hexamethyldisiloxane and 1.72 parts vinyl double-end cap, mix thoroughly, and add to the reactor. Set the temperature to 40°C and reflux for 30 minutes. After the liquid in the reactor refluxes for 30 minutes, quickly add a mixture of 60 parts sodium silicate and 120 parts distilled water, heat to 45°C, and hydrolyze for 3 hours. Then, add 130 parts hexamethyldisiloxane extract, set the temperature to 65°C, and extract for 1.5 hours. After extraction, allow the mixture to stand and separate. Remove the supernatant and wash it with 150 parts distilled water once or twice. Continue to let it stand and separate. Remove the supernatant to obtain approximately 170 parts of resin solution. Wash the resin solution with sodium carbonate solution until neutral, allow it to stand and separate. Remove the supernatant and add it to the reactor, heat and distill it to obtain resin powder.

[0088] Preparation of heavy peeling regulator: same as in Example 1.

[0089] Preparation of 13# release agent glue: same as Example 1.

[0090] 14# release agent glue solution configuration: same as in Example 1.

[0091] 15# release agent glue solution configuration: same as in Example 1.

[0092] Release agent glue coating and curing: the same as Example 1; the prepared release protective films are respectively recorded as 13# release protective film, 14# release protective film, and 15# release protective film of Comparative Example 2.

[0093] Release film testing: same as in Example 1.

[0094] Comparative Example 3 (Mixture of acetylene alcohol oligomer and butynol oligomer changed to ethynylcyclohexanol)

[0095] Synthesis of vinyl MQ resin: same as in Example 1.

[0096] Vinyl MQ resin modification: same as Example 1.

[0097] Preparation of a heavy-release agent: Add 65 parts of vinyl MQ resin to a reactor, add 25 parts of tetradecene, then add 10 parts of end-vinyl silicone oil with a viscosity of 1000 mPa·s and a vinyl content of 0.5%, and 1.5 parts of ethynyl cyclohexanol, and stir evenly to obtain a heavy-release agent.

[0098] Preparation of 16# release agent glue: same as Example 1.

[0099] 17# release agent glue solution configuration: same as in Example 1.

[0100] 18# release agent glue solution configuration: same as in Example 1.

[0101] Glue coating and curing: the same as in Example 1; the prepared release protective films are respectively recorded as 16# release protective film, 17# release protective film, and 18# release protective film of Comparative Example 3.

[0102] Release film testing: same as in Example 1.

[0103] Table 1 Performance test results of 1# glue solution, 2# glue solution and 3# glue solution in Example

[0104]

[0105] Table 2 Performance test results of 1# glue solution, 2# glue solution and 3# glue solution of comparative example

[0106]

[0107] The performance test standards and methods of the above-mentioned heavy release conditioning agent are as follows: the release force refers to FTM10; the residual adhesion rate refers to FTM11.

[0108] The calculation method of 70℃ aging climbing rate (%) is: 70℃ aging climbing rate (%) = {[release force (g / 25mm) / (70℃*20h+25℃*4h)]-[release force (g / 25mm) / (20min)]} / [release force (g / 25mm) / (20min)].

[0109] 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.

[0110] 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 silicone heavy release agent, characterized in that: The components include: 60-80 parts by weight of modified vinyl MQ resin, 10-30 parts by weight of diluent, 1-2 parts by weight of inhibitor and 5-10 parts by weight of vinyl polysiloxane; wherein the inhibitor is an acetylene alcohol oligomer, and the acetylene alcohol oligomer is selected from at least one of acetylene alcohol oligomer, butynol oligomer, ethynylcyclohexanol oligomer or hexynol oligomer; the modified vinyl MQ resin has a vinyl content of 0.3-2%; the vinyl polysiloxane has a vinyl content of 0.5-1.5%; and the diluent is a long-chain olefin. The modified vinyl MQ resin is prepared by the following method: adding hexamethyldisilazane and alcohol substances into the vinyl MQ resin, and performing hydrolysis condensation reaction at 40-60° C. to prepare the modified vinyl MQ resin.

2. The organosilicon heavy release agent according to claim 1, characterized in that: The modified vinyl MQ resin has a weight average molecular weight of 3000 to 8000; The diluent is C 12 ~C 20 at least one of olefins; The vinyl polysiloxane is a terminal vinyl polysiloxane with a viscosity of 500 to 50,000 mPa·s.

3. The organosilicon heavy release agent according to claim 2, characterized in that: The modified vinyl MQ resin has a weight average molecular weight of 4000 to 6000; The molecular structure of the terminal vinyl polysiloxane is Wherein: Vi is vinyl, R is vinyl or methyl, x, y, z are all natural numbers, 0≤x≤5, 1≤y≤4, 0≤z≤5.

4. An organosilicon heavy release agent according to claim 1 or 2, characterized in that: The preparation method of the modified vinyl MQ resin comprises the following steps: adding 25 to 50 parts of toluene to 100 parts of vinyl MQ resin and stirring to dissolve; after the resin is completely dissolved, adding 1 to 4 parts of hexamethyldisilazane, 0.5 to 2 parts of alcohol, and 0.5 to 2 parts of distilled water; heating the mixture to 40 to 60° C. and hydrolyzing and condensing the mixture for 2 to 3 hours; and finally heating the hydrolyzed and condensed resin to 100 to 110° C. and distilling the mixture to obtain the modified vinyl MQ resin.

5. The organosilicon heavy release agent according to claim 4, characterized in that: The alcohol substance is at least one of isopropyl alcohol, methanol, ethylene glycol, glycerol or n-butanol.

6. The method for preparing an organosilicon heavy release agent according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: (1) adding the modified vinyl MQ resin into a reaction kettle; (2) adding a diluent and stirring evenly; (3) adding vinyl polysiloxane and stirring evenly; and (4) adding an inhibitor and stirring evenly.

7. The organosilicon heavy release agent according to any one of claims 1 to 5 is used as an auxiliary agent of an organosilicon release agent, or as a release agent alone.

8. A method for preparing a release protective film, characterized in that: The preparation method comprises the following steps: 1) Preparation of release agent adhesive: Mix 100 parts of a heavy release agent and 0-300 parts of a release agent and stir evenly; add 2.5-10 parts of a cross-linking agent, based on the total weight of the heavy release agent and the release agent, while slowly stirring, and stir for 2-10 minutes; then add 1.5-6 parts of an anchoring agent and stir for 2-10 minutes; finally, add 1.5-6 parts of a catalyst and stir for 10-30 minutes to prepare an adhesive; wherein the heavy release agent is the silicone heavy release agent according to any one of claims 1 to 3; 2) Release agent glue coating and curing: first apply the glue evenly on the substrate, then cure the substrate coated with the glue at 90-120℃ for 10-30 seconds to obtain the release protective film.

9. A release protective film, characterized in that: The release protective film is prepared by the method according to claim 8.

10. The release protective film according to claim 9, characterized in that: The dry silicon content of the release protective film is 0.1 to 2 g / m 2 .

11. A release protective film according to claim 9 or 10, characterized in that: When the heavy release regulator and the silicone release agent are used together, when the addition amount of the heavy release regulator is 5 to 90%, the initial release force of the resulting release protective film is 30 to 800 g / 25 mm, the release force aging increase at 70°C is less than 30%, and the residual adhesion rate after aging at 70°C is ≥90%.

12. A release protective film according to claim 9 or 10, characterized in that: When the heavy release regulator is used alone, the initial release force of the resulting release protective film is ≥1000 g / 25 mm, the release force increases by less than 50% after aging at 70° C., and the residual adhesion rate after aging at 70° C. is ≥50%.

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