An emulsion-type release agent and its preparation method

Abstract

This application discloses an emulsion-type release agent and its preparation method. The release agent comprises the following raw materials in the indicated mass percentages: 5-15 wt% linear vinyl silicone oil, 5-15 wt% Q-type vinyl silicone oil, 15-20 wt% T-type vinyl silicone oil, 1-3 wt% hydrogen-containing silicone oil, 0.2-1 wt% anchoring agent, 0.3-1 wt% polyether-modified silicone oil, 10-50 ppm platinum catalyst, 200-1000 ppm inhibitor, and the balance being deionized water. This application, through the synergistic effect of vinyl silicone oils with different molecular configurations, yields a release agent with a release force of 5-20.0 g / inch and exhibiting high interfacial bonding strength and cohesive strength in adhesion tests, thus balancing the product performance requirements of high anchoring force and low release force.

Description

Technical Field

[0001] This application relates to the field of release agents, and in particular to an emulsion-type release agent and its preparation method. Background Technology

[0002] Traditional solvent-based release agents face severe pressure to be replaced due to their content of 40%-60% highly volatile organic solvents such as toluene and acetone. While solvent-free silicone oils offer advantages in terms of environmental friendliness, in the high-speed coating of film substrates such as polyester (PET) and biaxially oriented polypropylene (BOPP), limitations imposed by existing coating equipment and downstream application demands mean that some applications still rely on solvent-based or emulsion-based products. Replacing solvent-based release agents with emulsion-based release agents not only meets environmental requirements but also effectively reduces production costs.

[0003] Traditional silicone emulsion release agents typically use a single-molecule vinyl silicone polymer (vinyl silicone oil) as the main body of the release agent, which is then emulsified to form an emulsion-type release agent. This type of release agent struggles to simultaneously meet the application requirements of low release force (bonding strength with adhesives and other bonding materials) and high anchoring force (bonding strength with the substrate). Summary of the Invention

[0004] This application provides an emulsion-type release agent and its preparation method, which, through the synergy of vinyl silicone oils with different molecular configurations, yields a release agent coating with a release force of 5 to 20.0 g / inch and exhibits high interfacial bonding strength and cohesive strength in adhesion tests, thus meeting the product performance requirements of both high anchoring force and low release force.

[0005] In a first aspect, this application provides an emulsion-type release agent comprising the following raw materials in weight percentages:

[0006] Linear vinyl silicone oil 5-15 wt%, Q-type vinyl silicone oil 5-15 wt%, T-type vinyl silicone oil 15-20 wt%, hydrogen-containing silicone oil 1-3 wt%, anchoring agent 0.2-1 wt%, polyether modified silicone oil 0.3-1 wt%, platinum catalyst 10-50 ppm, inhibitor 200-1000 ppm, deionized water balance.

[0007] The molecular structure of the linear vinyl silicone oil of this application is as follows, where m≥1 and n≥0.

[0008]

[0009] The molecular structure of the T-type vinyl silicone oil of this application is as follows, where k≥1, m≥1, n≥1.

[0010]

[0011] The molecular structure of the Q-type vinyl silicone oil of this application is as follows, where n≥1.

[0012]

[0013] In any of the above technical solutions, the viscosity of the emulsion-type release agent is 100-300 cps, and the solid content is 38-42%.

[0014] In any of the above technical solutions, the kinematic viscosity of the linear vinyl silicone oil is 250–400 mm. 2 / s, vinyl content 1.0–2.0 wt%.

[0015] In any of the above technical solutions, the kinematic viscosity of the linear vinyl silicone oil is 300-500 mm. 2 / s, vinyl content 1.0–2.0 wt%.

[0016] In any of the above technical solutions, the kinematic viscosity of the linear vinyl silicone oil is 300-500 mm. 2 / s, vinyl content 1.0–2.0 wt%.

[0017] This application addresses the contradiction between low release force and high anchoring force in traditional single-configuration silicones by combining linear, T-type (branched), and Q-type (star-shaped) vinyl silicone oils. Q-type and T-type silicone oils, due to their three-dimensional structure, exhibit high reactivity with hydrogen-containing silicone oils, forming a dense, high-cohesive-strength framework after curing. However, in practical applications, they demonstrate poor substrate anchoring force and are prone to interfacial damage (interfacial peeling) during adhesion testing. Linear silicone oils, with their flexible molecular chains enhancing wettability and van der Waals forces, significantly improve adhesion; however, when used alone, they have a slow crosslinking rate and low cohesive strength in the cured layer, making them prone to cohesive failure (release coating cracking) during adhesion testing. The combination of these three types of silicone oils provides a rapid crosslinking framework, while the linear silicone oil fills network gaps and strengthens interfacial adhesion, resulting in a release agent layer with both high cohesive strength and interfacial bonding strength, thus achieving high anchoring force. In addition, the release force of the compounded release agent is lower than that of the traditional single-configuration release agent, and can be controlled to be no higher than 20.0 g / inch.

[0018] In any of the above technical solutions, the raw material further includes 0.5 to 1.0 wt% of modified hydrogen-containing silicone oil, which is prepared by hydrosilylation of side-containing hydrogen-containing silicone oil and fluorinated acrylate, wherein the molar ratio of hydrogen groups to fluorinated acrylate in the side-containing hydrogen-containing silicone oil is 1:0.4 to 0.6.

[0019] In any of the above technical solutions, the fluorinated acrylate is selected from at least one of trifluoroethyl acrylate, trifluoroethyl methacrylate, and perfluoroalkyl acrylate.

[0020] The molecular structure of the hydrogen-containing silicone oil of this application is shown below, where n≥1.

[0021]

[0022] This application utilizes a modified hydrogen-containing silicone oil prepared by hydrosilylation of side-chain hydrogen-containing silicone oil and fluorinated acrylate. Fluorinated groups are introduced into the side chains of the hydrogen-containing silicone oil, resulting in extremely low surface energy. During curing, these groups spontaneously migrate to the air interface of the release layer, reducing the bonding energy with the adhesive material and further lowering the release force, thus meeting the product requirements for high anchoring strength and low release force. This is significantly different from conventional hydrofluorosilicone oils, which are typically obtained by ring-opening copolymerization of fluorinated cyclohydrosilanes and hydrogen-containing silicone oil, or by co-hydrolysis of fluorinated chlorosilanes and hydrochlorosilanes; the fluorinated groups are usually embedded in the silicone oil backbone. In contrast, the fluorinated groups in this modified silicone oil are only connected to the side chains through flexible alkane chains, without disrupting the polarity of the siloxane backbone. Its enrichment behavior is driven by interfacial energy and has almost no impact on the chemical bonding between the release layer and substrates such as PET, thus maintaining high anchoring strength. Hydrofluoric silicone oils with fluorine-containing main chains hinder interfacial reactions with the substrate due to the fluorine atoms being embedded in the backbone, weakening the chemical bond with the substrate and easily causing a simultaneous decrease in anchoring force and release force.

[0023] It is worth noting that the modified hydrogen-containing silicone oil of this application has reactive silane groups, which can participate in the cross-linking and curing reaction with vinyl silicone oil, and is less likely to precipitate and contaminate the product with the release film.

[0024] In any of the above technical solutions, the anchoring agent is epoxy-vinyl modified nano-silica.

[0025] In any of the above technical solutions, the raw materials of the epoxy-vinyl modified nano silica, by mass, include: 10 parts of nano silica, 4-6 parts of orthosilicate compound, 2-3 parts of epoxy siloxane compound, and 1-3 parts of vinyl siloxane compound; the orthosilicate compound is modified on the surface of the nano silica, and then hydrolyzed and polycondensed with the epoxy siloxane compound and the vinyl siloxane compound.

[0026] In any of the above technical solutions, the preparation steps of the epoxy-vinyl modified nano-silica are as follows:

[0027] Nano-silica was dispersed in ethanol to obtain a suspension; an orthosilicate ethanol solution with a pH of 3-4 was added dropwise to the suspension for surface modification to obtain an intermediate solution;

[0028] Epoxysiloxane compound and vinylsiloxane compound were dissolved in ethanol, and a pH adjuster was added to adjust the pH to 3-4. Pre-hydrolysis was carried out for 10-30 min to obtain a pre-hydrolyzed mixture.

[0029] The pre-hydrolyzed mixture is added dropwise to the intermediate solution, and the temperature is raised to 50-60℃ to carry out a polycondensation reaction. After the reaction is completed, a neutralizing agent is added until the pH is neutral. After centrifugation, washing, and drying, the product is obtained.

[0030] In any of the above technical solutions, the epoxy siloxane compound is selected from γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane.

[0031] In any of the above technical solutions, the vinylsiloxane compound is selected from vinyltrimethoxysilane or vinyltriethoxysilane.

[0032] In any of the above technical solutions, the orthosilicate is selected from methyl orthosilicate or ethyl orthosilicate.

[0033] In any of the above technical solutions, the concentration of the orthosilicate ethanol solution is not higher than 10 wt%, preferably 5 to 10 wt%.

[0034] In any of the above technical solutions, the reaction time for surface modification is 2 to 4 hours.

[0035] In any of the above technical solutions, the polycondensation reaction takes 4 to 6 hours.

[0036] The anchoring agent of this application has a core-shell structure. Specifically, under acidic conditions, tetraethyl orthosilicate (TEOS) preferentially condenses with the silanol groups on the surface of nano-SiO2 to form a Si-O-Si(OC2H5)3 bridging layer, which inhibits TEOS self-polymerization while increasing surface reaction sites. Pre-hydrolyzed epoxy silane and vinyl silane are grafted on the transition layer to form a hybrid shell containing epoxy groups, vinyl groups and residual silanol groups. The various functional groups of this hybrid shell can form strong chemical bonds with the release agent host (such as vinyl) and the substrate (such as epoxy group), respectively, thereby improving the anchoring performance of the release agent.

[0037] Secondly, this application provides a method for preparing an emulsion-type release agent, which involves mixing linear vinyl silicone oil, Q-type vinyl silicone oil, T-type vinyl silicone oil, hydrogen-containing silicone oil, anchoring agent, polyether-modified silicone oil, platinum catalyst, inhibitor, deionized water, and other raw materials according to the raw material ratio of any of the above-mentioned release agents, and then performing homogenization treatment to obtain the release agent.

[0038] In summary, this application has the following beneficial effects:

[0039] This application presents a release agent crosslinking system constructed by compounding linear, Q-type, and T-type vinyl silicone oils with hydrogen-containing silicone oils. This system combines advantages such as high crosslinking rate, strong cohesive strength, and excellent interfacial bonding, ultimately achieving high anchoring force. Furthermore, it reduces the release force to ≤20.0 g / inch. This release agent is suitable for the production of release films in fields such as electronic components and food. Detailed Implementation

[0040] Preparation Example

[0041] Preparation Example 1-1: A modified hydrogen-containing silicone oil was prepared according to the following steps:

[0042] 1000g of SH-50 hydrogen-containing silicone oil with a hydrogen content of 0.5% (calculated hydrogen content of 5mol) and 1330.5g (2.5mol) of perfluorooctylpropyl acrylate were added to a reactor. The reactor was purged with nitrogen to remove air, and the temperature was raised to 110℃. 20ppm of caster platinum catalyst (calculated as Pt) was added dropwise, and the reaction temperature was maintained at 110℃±2℃, with stirring for 4 hours. After the reaction was completed, the temperature was raised to 130℃, and the mixture was distilled under reduced pressure (-0.1MPa) for 1.5 hours to remove low-molecular-weight impurities, yielding the modified hydrogen-containing silicone oil.

[0043] Preparation Examples 1-2: A modified hydrogen-containing silicone oil was prepared according to the following steps:

[0044] 1000g of SH-36 hydrogen-containing silicone oil with a hydrogen content of 0.25% (calculated hydrogen content of 2.5mol) and 418.2g (1mol) of perfluorohexyl ethyl acrylate were added to a reactor. The reactor was purged with nitrogen to remove air, and the temperature was raised to 105℃. 10ppm of caster platinum catalyst (calculated as Pt) was added dropwise, and the reaction temperature was maintained at 105℃±2℃. The mixture was stirred for 4 hours. After the reaction was completed, the temperature was raised to 130℃, and the mixture was distilled under reduced pressure (-0.1MPa) for 1 hour to remove low-molecular-weight impurities, yielding the modified hydrogen-containing silicone oil.

[0045] Preparation Examples 1-3: A modified hydrogen-containing silicone oil was prepared according to the following steps:

[0046] 1000g of SH-75 hydrogen-containing silicone oil with a hydrogen content of 0.75% (calculated hydrogen content of 7.5mol) and 693.4g (4.5mol) of trifluoroethyl acrylate were added to a reactor. The reactor was purged with nitrogen to remove air, and the temperature was raised to 110℃. 30ppm of caster platinum catalyst (calculated as Pt) was added dropwise, and the reaction temperature was maintained at 110℃±2℃. The mixture was stirred for 5 hours. After the reaction was completed, the temperature was raised to 140℃, and the mixture was distilled under reduced pressure (-0.1MPa) for 1.5 hours to remove low-molecular-weight impurities, yielding the modified hydrogen-containing silicone oil.

[0047] Preparation Examples 1-4: 1000g of end-side hydrogen-containing silicone oil DSH-28 (calculated hydrogen content of 2.8mol) with a hydrogen content of 0.28% was added to a reactor along with 468.4g (1.12mol) of perfluorohexylethyl acrylate. The reactor was purged with nitrogen to remove air, and the temperature was raised to 105℃. 10ppm of caster platinum catalyst (based on Pt) was added dropwise, and the reaction temperature was maintained at 105℃±2℃. The reaction was stirred for 4 hours. After the reaction was completed, the temperature was raised to 130℃, and the mixture was distilled under reduced pressure (-0.1MPa) for 1 hour to remove low-molecular-weight impurities, yielding the modified hydrogen-containing silicone oil.

[0048] Preparation Example 2-1, Anchoring Agent, was prepared according to the following steps:

[0049] 100g of nano-silica was dispersed in 150g of ethanol and sonicated for 30 minutes to form a homogeneous suspension. 50g of tetraethyl orthosilicate was mixed with 50g of ethanol, and an acetic acid-water solution (acetic acid:water = 1:50, v / v) was added dropwise to adjust the pH to 3.5–4.0, yielding an orthosilicate ethanol solution. This orthosilicate ethanol solution was added dropwise to the suspension at a rate of 2mL / min, with the temperature maintained at ≤10℃ in an ice bath during the addition. After the addition was complete, the temperature was raised to 25℃, and the reaction was allowed to proceed for 3 hours to obtain an intermediate solution.

[0050] Dissolve 20g of γ-glycidoxypropyltrimethoxysilane and 20g of vinyltrimethoxysilane in 100g of ethanol; add acetic acid to adjust the pH to 4.0, and pre-hydrolyze at 25°C for 15 minutes to generate a partially hydrolyzed pre-hydrolyzed mixture, which can avoid the rapid polycondensation caused by direct addition.

[0051] The pre-hydrolyzed mixture was added dropwise (1 mL / min) to the intermediate solution. After the addition was complete, the temperature was raised to 50 °C and the reaction was carried out for 5 hours (during the reaction, the pH of the system was adjusted to 3.5–4.0 using acetic acid). After the reaction was completed, triethylamine was added to neutralize the system to pH 7.0, and the reaction was terminated. The mixture was centrifuged and washed three times with ethanol-water (1:1) to remove unreacted monomers. The mixture was then vacuum dried at 60 °C for 10 hours to obtain epoxy-vinyl modified nano-silica.

[0052] Preparation Example 2-2, Anchoring Agent, prepared according to the following steps:

[0053] 100g of nano-silica was dispersed in 150g of ethanol and sonicated for 30 minutes to form a homogeneous suspension. 40g of tetraethyl orthosilicate was mixed with 60g of ethanol, and an acetic acid-water solution (acetic acid:water = 1:50, v / v) was added dropwise to adjust the pH to 3.5–4.0, yielding an orthosilicate ethanol solution. This orthosilicate ethanol solution was added dropwise to the suspension at a rate of 2mL / min, with the temperature maintained at ≤10℃ in an ice bath during the addition. After the addition was complete, the temperature was raised to 25℃, and the reaction was allowed to proceed for 3 hours to obtain an intermediate solution.

[0054] Dissolve 30g of γ-glycidoxypropyltriethoxysilane and 10g of vinyltriethoxysilane in 100g of ethanol; add acetic acid to adjust the pH to 4.0, and pre-hydrolyze at 25°C for 10 minutes to generate a partially hydrolyzed pre-hydrolyzed mixture, which can avoid the rapid polycondensation caused by direct addition.

[0055] The pre-hydrolyzed mixture was added dropwise (2 mL / min) to the intermediate solution. After the addition was complete, the temperature was raised to 50 °C and the reaction was carried out for 4 hours (during the reaction, the pH of the system was adjusted to 3.5–4.0 using acetic acid). After the reaction was complete, triethylamine was added to neutralize the system to pH 7.0, and the reaction was terminated. The mixture was centrifuged and washed three times with ethanol-water (1:1) to remove unreacted monomers. The mixture was then vacuum dried at 60 °C for 10 hours to obtain epoxy-vinyl modified nano-silica.

[0056] Preparation Example 2-3, Anchoring Agent, prepared according to the following steps:

[0057] 100g of nano-silica was dispersed in 150g of ethanol and sonicated for 30 minutes to form a homogeneous suspension. 60g of methyl orthosilicate was mixed with 60g of ethanol, and an acetic acid-water solution (acetic acid:water = 1:50, v / v) was added dropwise to adjust the pH to 3.0–3.5, yielding an orthosilicate ethanol solution. This orthosilicate ethanol solution was added dropwise to the suspension at a rate of 3mL / min, with the temperature maintained at ≤10℃ in an ice bath during the addition. After the addition was complete, the temperature was raised to 25℃, and the reaction was allowed to proceed for 4 hours to obtain an intermediate solution.

[0058] Dissolve 20g of γ-glycidoxypropyltrimethoxysilane and 30g of vinyltriethoxysilane in 100g of ethanol; add acetic acid to adjust the pH to 3.0, and pre-hydrolyze at 25°C for 30 minutes to generate a partially hydrolyzed pre-hydrolyzed mixture, which can avoid the rapid polycondensation caused by direct addition.

[0059] The pre-hydrolyzed mixture was added dropwise (2 mL / min) to the intermediate solution. After the addition was complete, the temperature was raised to 50 °C and the reaction was carried out for 4–6 hours (during the reaction, the pH of the system was adjusted to 3.5–4.0 using acetic acid). After the reaction was complete, triethylamine was added to neutralize the system to pH 7.0, and the reaction was terminated. The mixture was centrifuged and washed three times with ethanol-water (1:1) to remove unreacted monomers. The mixture was then vacuum dried at 60 °C for 10 hours to obtain epoxy-vinyl modified nano-silica.

[0060] Preparation Example 2-4, the anchoring agent, differs from Preparation Example 2-1 in that an equal amount of γ-glycidoxypropyltrimethoxysilane is used instead of vinyltrimethoxysilane.

[0061] Preparation Example 2-5, the anchoring agent, differs from Preparation Example 2-1 in that an equal amount of vinyltrimethoxysilane is used instead of γ-glycidoxypropyltrimethoxysilane.

[0062] Preparation Example 2-6, anchoring agent, differs from Preparation Example 2-1 in that an equal amount of γ-glycidoxypropyltrimethoxysilane is used instead of tetraethyl orthosilicate.

[0063] Preparation Example 2-7, Anchoring Agent, prepared according to the following steps:

[0064] Mix 50g of tetraethyl orthosilicate with 50g of ethanol, and add dropwise an acetic acid-water solution (acetic acid:water = 1:50, v / v) to adjust the pH to 3.5-4.0 to obtain an orthosilicate ethanol solution.

[0065] Dissolve 20g of γ-glycidoxypropyltrimethoxysilane and 20g of vinyltrimethoxysilane in 100g of ethanol; add acetic acid to adjust the pH to 4.0, and pre-hydrolyze at 25°C for 15 minutes to generate a partially hydrolyzed pre-hydrolyzed mixture, which can avoid the rapid polycondensation caused by direct addition.

[0066] The pre-hydrolyzed mixture was added dropwise (1 mL / min) to the orthosilicate ethanol solution. After the addition was complete, the temperature was raised to 50 °C and the reaction was carried out for 5 hours (during the reaction, the pH of the system was adjusted to 3.5–4.0 using acetic acid). After the reaction was completed, triethylamine was added to neutralize the system to pH 7.0.

[0067] Example

[0068] The vinyl silicone oils in the following examples were obtained from Hangzhou Chongyao, wherein the viscosity of the linear vinyl silicone oil is 350 mm. 2 / s, vinyl content is 1.4wt%; viscosity of type T vinyl silicone oil is 380mm. 2 / s, vinyl content is 1.2wt%; Q-type vinyl silicone oil viscosity is 380mm. 2 / s, vinyl content is 1.2wt%. The polyether-modified silicone oil is Hangzhou Chongyao PC-0190; the inhibitor is 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane.

[0069] Example 1: An emulsion-type release agent was prepared according to the following steps:

[0070] 1 kg of linear vinyl silicone oil, 1 kg of Q-type vinyl silicone oil, 1.8 kg of T-type vinyl silicone oil, 0.2 kg of hydrogen-containing silicone oil (hydrogen content 1.0%, viscosity 10-20 mPa.s), 0.08 kg of modified hydrogen-containing silicone oil from Preparation Example 1-1, 0.05 kg of anchoring agent from Preparation Example 2-1, 0.05 kg of polyether-modified silicone oil, 30 ppm of caster platinum catalyst, and 500 ppm of inhibitor were simultaneously added to a high-speed disperser and dispersed evenly. Then, 5.9 kg of deionized water was added in three equal portions. After phase inversion, the mixture was transferred to a high-pressure homogenizer and homogenized three times at 30 MPa to obtain the final product.

[0071] Example 2, an emulsion-type release agent, prepared according to the following steps:

[0072] 1.5 kg of linear vinyl silicone oil, 0.5 kg of Q-type vinyl silicone oil, 1.5 kg of T-type vinyl silicone oil, 0.1 kg of hydrogen-containing silicone oil (0.8% hydrogen content, viscosity 20-50 mPa·s), 0.05 kg of modified hydrogen-containing silicone oil from Preparation Examples 1-2, 0.1 kg of anchoring agent from Preparation Example 2-2, 0.03 kg of polyether-modified silicone oil, 10 ppm of caster platinum catalyst, and 200 ppm of inhibitor were simultaneously added to a high-speed disperser and dispersed evenly. Then, 5.9 kg of deionized water was added in three equal portions. After phase inversion, the mixture was transferred to a high-pressure homogenizer and homogenized three times at 30 MPa to obtain the final product.

[0073] Example 3: An emulsion-type release agent was prepared according to the following steps:

[0074] 0.5 kg of linear vinyl silicone oil, 1.5 kg of Q-type vinyl silicone oil, 2.0 kg of T-type vinyl silicone oil, 0.3 kg of hydrogen-containing silicone oil (hydrogen content 1.2%, viscosity 10-20 mPa.s), 0.1 kg of modified hydrogen-containing silicone oil from Preparation Examples 1-3, 0.02 kg of anchoring agent from Preparation Examples 2-3, 0.1 kg of polyether-modified silicone oil, 50 ppm of caster platinum catalyst, and 1000 ppm of inhibitor were simultaneously added to a high-speed disperser and dispersed evenly. Then, 5.9 kg of deionized water was added in three equal portions. After phase inversion, the mixture was transferred to a high-pressure homogenizer and homogenized three times at 30 MPa to obtain the final product.

[0075] Example 4, an emulsion-type release agent, differs from Example 1 in that an equal amount of modified hydrogen-containing silicone oil obtained from Preparation Examples 1-4 is used to replace the modified hydrogen-containing silicone oil of Preparation Example 1-1.

[0076] Example 5, an emulsion-type release agent, differs from Example 1 in that an equal amount of hydrogen-containing silicone oil (hydrogen content 1.0%, viscosity 10-20 mPa.s) is used to replace the modified hydrogen-containing silicone oil in Preparation Example 1-1.

[0077] Example 6, an emulsion-type release agent, differs from Example 1 in that an equal amount of the anchoring agent of Preparation Example 2-4 is used to replace the anchoring agent of Preparation Example 2-1.

[0078] Example 7, an emulsion-type release agent, differs from Example 1 in that an equal amount of the anchoring agent of Preparation Example 2-5 is used to replace the anchoring agent of Preparation Example 2-1.

[0079] Example 8, an emulsion-type release agent, differs from Example 1 in that an equal amount of the anchoring agent of Preparation Examples 2-6 is used instead of the anchoring agent of Preparation Example 2-1.

[0080] Example 9, an emulsion-type release agent, differs from Example 1 in that an equal amount of the anchoring agent of Preparation Examples 2-7 is used to replace the anchoring agent of Preparation Example 2-1.

[0081] Comparative Example

[0082] Comparative Example 1, an emulsion-type release agent, differs from Example 9 in that an equal amount of linear vinyl silicone oil is used instead of Q-type vinyl silicone oil.

[0083] Comparative Example 2, an emulsion-type release agent, differs from Example 9 in that an equal amount of Q-type vinyl silicone oil is used instead of linear vinyl silicone oil.

[0084] Comparative Example 3, an emulsion-type release agent, differs from Example 9 in that an equal amount of linear vinyl silicone oil is used instead of T-type vinyl silicone oil and Q-type vinyl silicone oil.

[0085] Comparative Example 4, an emulsion-type release agent, differs from Example 9 in that an equal amount of T-type vinyl silicone oil is used instead of linear vinyl silicone oil and Q-type vinyl silicone oil.

[0086] Comparative Example 5, an emulsion-type release agent, differs from Example 9 in that an equal amount of Q-type vinyl silicone oil is used instead of linear vinyl silicone oil and T-type vinyl silicone oil.

[0087] Performance testing

[0088] Test 1: Release force test (180° peel test)

[0089] Sample preparation: The release agent was uniformly coated onto a 38µm glossy PET substrate, with a wet coating amount of 0.3 g / m. 2 Cur at 130℃ for 30 seconds; after coating, place in an environment of 25℃ and 50% humidity for 24 hours to ensure complete curing.

[0090] Test method: Take an A4-sized sample and cut a 25mm wide strip. 7475 tape was adhered to the release layer surface and rolled three times with a 2kg standard pressure roller at a speed of 10mm / s. The resulting strip was cut to approximately 3cm wide and aged in a 70℃ oven for 20 hours. Afterward, it was placed in a constant temperature and humidity chamber (temperature (23±1)℃, relative humidity 50%±5%) for approximately 30 minutes. An FPT-F1 friction coefficient / peel tester was then used for testing. One end of the strip was peeled off, and paper tape was attached to the exposed end of the 7475 tape. The other end of the paper tape was clamped into the left peeling clamp. A sharp corner was cut from the lower substrate to be clamped into the eccentric wheel of the right peeling clamp. The position of the strip was adjusted to ensure that the paper tape did not contact the strip and that the peeling direction was aligned with the center of the sensor's force hole. After heat aging at 70℃ for 20 hours, the sample was placed in a constant temperature and humidity chamber (25℃, 50%RH) for equilibration for 1 hour. The tester was started, and the release force was tested at a speed of 300 mm / min and a peel angle of 180°. The peel force-time curve (unit: N) was recorded, and the average value of three parallel tests was taken and converted into release force (unit: gf / inch): Release force (g / inch) = [average peel force (N) × 101.97] / sample peel width (inch).

[0091] Experiment 2: Anchoring Force Test

[0092] Sample preparation: The release agent was uniformly coated onto a 38µm glossy PET substrate, with a wet coating amount of 1.0 ± 0.1 g / m². 2 Cur at 130℃ for 30 seconds; after coating, place in an environment of 25℃ and 50% humidity for 24 hours to ensure complete curing.

[0093] Test method: 25mm wide VHB tape is applied to the surface of the release layer and rolled three times with a pressure roller. After curing at room temperature for 24 hours, the sample is clamped in a universal testing machine and peeled off at 90° (tape-release layer interface) at a speed of 100 mm / min. The maximum force value during the peeling process is recorded (unit: N / 25 mm), and the average value of the three peels is taken as the adhesion (anchoring force) strength.

[0094] Determination of damage type:

[0095] Interface failure: The release layer peels off completely from the substrate surface (substrate exposure >80%), indicating that insufficient anchoring force is the main factor in release layer peeling.

[0096] Cohesive failure: internal fracture of the release layer (>20% coating residue on the substrate surface) indicates that insufficient cohesive strength is the main factor in release layer peeling.

[0097] Table 1. Results of Release Agent Performance Tests

[0098]

[0099]

[0100] Compared to Examples 1-9, Comparative Examples 1-5 all showed a decrease in adhesion (anchoring) along with fluctuations in release force, proving that single Q-type, T-type, or linear silicone oils have defects in coating cohesive strength or interfacial bonding strength, resulting in a decrease in overall adhesion.

[0101] Example 4 (using end-side hydrogen-containing silicone oil) showed a decrease in release force to 11.0 g / inch and adhesion to 2.2 N / 25 mm compared to Example 2. ， This indicates that the introduction of fluorinated end groups causes a simultaneous decrease in release force and adhesion, with a more significant decrease in adhesion, thus affecting the anchoring performance of the release agent. This may be because the fluorine atoms in the main chain of the hydrofluorosilicone oil, due to their embedding in the backbone, hinder the interfacial reaction with the substrate, weakening the chemical bond with the substrate and easily leading to a simultaneous decrease in anchoring force and release force. In Example 5 (unmodified hydrofluorosilicone oil), the release force increased to 19.8 g / inch compared to Example 1, indicating that fluorinated acrylate modification significantly reduces tape bonding strength by lowering surface energy (10-15 mN / m). This may be because the fluorinated side chain groups can accumulate and arrange themselves at the air interface, reducing van der Waals forces with the adhesive.

[0102] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. An emulsion-type release agent characterized by comprising, The raw materials include the following mass percentages: linear vinyl silicone oil 5-15 wt%, Q-type vinyl silicone oil 5-15 wt%, T-type vinyl silicone oil 15-20 wt%, hydrogen-containing silicone oil 1-3 wt%, modified hydrogen-containing silicone oil 0.5-1.0 wt%, anchoring agent 0.2-1 wt%, polyether-modified silicone oil 0.3-1 wt%, platinum catalyst 10-50 ppm, inhibitor 200-1000 ppm, deionized water in remainder; The modified hydrogen-containing silicone oil is prepared by silicon-hydrogen addition of side hydrogen-containing silicone oil and fluorine-containing acrylic ester, and the molar ratio of hydrogen groups in the side hydrogen-containing silicone oil to the fluorine-containing acrylic ester is 1:0.4-0.

6. The anchoring agent is epoxy-vinyl modified nano-silica, and the raw materials thereof include: nano-silica 10 parts, orthosilicate compound 4-6 parts, epoxy siloxane compound 2-3 parts, and vinyl siloxane compound 1-3 parts; the orthosilicate compound is modified on the surface of nano-silica, and then hydrolytic polycondensation reaction is carried out with the epoxy siloxane compound and the vinyl siloxane compound.

2. The emulsion-type release agent according to claim 1, characterized by, The viscosity of the emulsion type release agent is 100-300 cps, and the solid content is 38-42%.

3. The emulsion-type release agent according to claim 1, wherein The fluorine-containing acrylic ester is at least one selected from trifluoroethyl acrylate, trifluoroethyl methacrylate and perfluoroalkyl acrylate.

4. The emulsion-type release agent according to claim 1, wherein The preparation steps of the epoxy-vinyl modified nano-silica are as follows: nano-silica is dispersed in ethanol to obtain a suspension; the ethanol solution of the orthosilicate compound with pH 3-4 is added dropwise to the suspension for surface modification to obtain an intermediate solution; the epoxy siloxane compound and the vinyl siloxane compound are dissolved in ethanol, a pH adjuster is added to pH 3-4, and pre-hydrolysis is carried out for 10-30 min to obtain a pre-hydrolysis mixture; the pre-hydrolysis mixture is added dropwise into the intermediate solution, and the temperature is raised to 50-60℃ for polycondensation reaction; after the reaction is completed, a neutralizing agent is added to pH neutral, and then centrifugal separation, washing and drying are carried out.

5. The emulsion-type release agent according to claim 1, wherein The epoxy siloxane compound is selected from γ-glycidyl ether propyl trimethoxysilane or γ-glycidyl ether propyl triethoxysilane; and the vinyl siloxane compound is selected from vinyl trimethoxysilane or vinyl triethoxysilane.

6. The emulsion-type release agent according to claim 1, wherein The orthosilicate compound is selected from methyl orthosilicate or ethyl orthosilicate.

7. A method for producing an emulsion-type release agent, characterized by, The raw materials of the release agent according to any one of claims 1-6 are mixed, and then homogenized to obtain the release agent.

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