CN115612147B - Optical fluorine release film with multilayer structure and manufacturing method thereof - Google Patents
Optical fluorine release film with multilayer structure and manufacturing method thereof Download PDFInfo
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Abstract
The application relates to the technical field of release films, and particularly discloses an optical fluorine release film with a multilayer structure and a manufacturing method thereof. The optical fluorine release film with the multilayer structure comprises a PET substrate, a fluorine release layer 1 and a fluorine release layer 2, wherein the fluorine release layer 1 and the fluorine release layer 2 are arranged on the surface of the PET substrate; the fluorine release layer 1 comprises the following components in parts by weight: 30-50% of modified fluorine release agent, 0.2-5% of cross-linking agent, 0.1-3% of UV photoinitiator and the balance of fluorocarbon resin; the fluorine release layer 2 comprises: 30-50% of modified fluorine release agent, 0.2-5% of cross-linking agent, 0.1-3% of thermal catalyst and the balance of fluorocarbon resin; the modified fluorine release agent is prepared by reacting 10-hydroxydecenoic acid with dodecyl heptyl methacrylate under the catalysis of Ziegler-Natta catalyst and dodecyl mercaptan, so that the scratch resistance of the fluorine release film is improved.
Description
Technical Field
The application relates to the technical field of release films, in particular to an optical fluorine release film with a multilayer structure and a manufacturing method thereof.
Background
A release film refers to a film having a surface with separability, and the release film has no tackiness, or slight tackiness, after being contacted with a specific material under limited conditions.
The release film is widely applied to the industries of adhesive products, die cutting, punching processing and the like. The release film comprises a silicone oil release film, a fluorine release film and the like, and along with the application of the organic silicon pressure-sensitive adhesive in the fields of electronic circuits, medical treatment, optics, communication and the like, the use of the release film in the field of die cutting processing of the organic silicon pressure-sensitive adhesive is gradually increased. The silicone oil release film can react with the organic silicon pressure-sensitive adhesive to generate silicon transfer, so that the organic silicon pressure-sensitive adhesive loses viscosity, and therefore, the fluorine release film is used in the die cutting of the organic silicon pressure-sensitive adhesive.
The fluorine release film is obtained by coating a fluorine release agent on the surface of a PET substrate and curing the fluorine release agent. The fluorine release film has ultra-light release force, and the release force is in the range of 1-5 g/inch. In the die cutting process of the organic silicon pressure-sensitive adhesive, a fluorine release film is required to be adhered to the surface of the organic silicon pressure-sensitive adhesive, so that the organic silicon pressure-sensitive adhesive is protected. When the rotating roller is used for spreading the fluorine release film, the fluorine release layer is scratched, and the fluorine release layer is scratched to expose the substrate material. When the fluorine release film layer of the fluorine release film is used as a matrix to coat the organic silicon pressure-sensitive adhesive, the organic silicon pressure-sensitive adhesive can be in direct contact with the base material, so that the organic silicon pressure-sensitive adhesive is not easy to separate from the base material after adhesion, and the release effect of the fluorine release film is poor.
Disclosure of Invention
In order to reduce the situation that a fluorine release layer of a fluorine release film is scratched, so that the release force of the fluorine release film is large, the application provides an optical fluorine release film with a multilayer structure and a manufacturing method thereof.
The application provides an optical fluorine release film with a multilayer structure, which adopts the following technical scheme:
the utility model provides an optical fluorine is from type membrane with multilayer structure, includes PET substrate and sets up the fluorine from type layer 1 and the fluorine from type layer 2 that sets up on the fluorine from type layer 1 on PET substrate surface, according to parts by weight, fluorine is from type layer 1 including following component: 30-50% of modified fluorine release agent, 0.2-5% of cross-linking agent, 0.1-3% of UV photoinitiator and the balance of fluorocarbon resin; the fluorine release layer 2 comprises the following components: 30-50% of modified fluorine release agent, 0.2-5% of cross-linking agent, 0.1-3% of thermal catalyst and the balance of fluorocarbon resin;
the modified fluorine release agent comprises the following preparation raw materials in parts by weight: 30-40% of dodecaheptyl methacrylate, 10-15% of 10-hydroxydecenoic acid, 0.3-0.6% of ammonium persulfate, 0.1-1.5% of Ziegler-Natta catalyst, 0.1-1% of dodecyl mercaptan, 2-2.5% of emulsifier, 0.1-0.55% of standard pH buffering agent and the balance of deionized water; the preparation method of the modified fluorine release agent comprises the following steps: uniformly mixing ammonium persulfate with 25% -30% deionized water to prepare an ammonium persulfate aqueous solution; uniformly mixing the dodecyl heptyl methacrylate, 75% -80% of emulsifier and the rest deionized water to obtain a dodecyl heptyl methacrylate preparation liquid; uniformly mixing 15% -20% of dodecyl heptyl methacrylate preparation liquid, 30% -35% of ammonium persulfate aqueous solution, the rest of emulsifying agent, standard pH buffering agent and 40% -50% of deionized water, and heating for reaction for 25-35 min to obtain intermediate reaction liquid; adding dodecyl mercaptan and Ziegler-Natta catalyst into the intermediate reaction liquid, mixing uniformly, then uniformly mixing 10-hydroxydecenoic acid and the rest of the dodecyl heptyl methacrylate preparation liquid, dripping the rest of ammonium persulfate aqueous solution into the intermediate reaction liquid while dripping the rest of ammonium persulfate aqueous solution into the intermediate reaction liquid, raising the temperature to 85-90 ℃, reacting for 1-1.5 h, reducing the temperature to below 45 ℃, regulating the pH to be alkalescent, filtering and discharging to obtain the modified fluorine release agent.
By adopting the technical scheme, the fluorine-containing polyacrylate is synthesized by taking the dodecyl heptyl methacrylate and the 10-hydroxydecenoic acid as main raw materials. The 10-hydroxydecenoic acid is used as a crosslinking monomer, has longer chain segment for connecting hydroxyl, has higher degree of freedom, has more active reactivity and is convenient for crosslinking reaction. The connecting chains among the cross-linked polymers are longer, and the movement among polymer molecules is flexible, so that the toughness of the polymer is increased, and the deformation of a molecular chain network can be recovered in time when the external force is applied, thereby improving the scratch resistance of the modified fluorine release layer. The molecular chain segment of the dodecaheptyl methacrylate is longer, the steric hindrance occupied by the functional group is larger, and when the polymerization degree of the copolymer of the dodecaheptyl methacrylate and the 10-hydroxydecenoic acid reaches a certain degree, the polymerization reaction is difficult to continue. The Ziegler-Natta catalyst and the dodecyl mercaptan are matched to promote the polymerization of dodecyl methacrylate and 10-hydroxydecenoic acid to obtain longer polymer molecular chains, and meanwhile, the crosslinking degree between the polymer molecular chains is higher, so that the occurrence of side reactions in the reaction is reduced, the polymerization degree and purity of the product are ensured, and the release force of the fluorine rational membrane is ensured. In addition, the dodecyl mercaptan can reduce the occurrence of chain transfer reaction, so that the cross-linking positions of the fluorine-containing polyacrylic acid are uniformly distributed, the surface energy of the fluorine release layer is further reduced in a more compact and orderly manner, and the release force of the fluorine release film is further reduced.
Optionally, the emulsifier is one or more of polyoxyethylene nonylphenol ether ammonium sulfate emulsifier and polyoxyethylene nonylphenol ether emulsifier.
By adopting the technical scheme, the dodecyl methyl methacrylate can be stably dispersed in the water phase in the form of fine liquid drops by adopting the ammonium nonylphenol polyoxyethylene ether sulfate emulsifier and the mixed emulsifier of the nonylphenol polyoxyethylene ether emulsifier, so that the polymerization rate of the dodecyl methyl methacrylate and 10-hydroxydecenoic acid can be improved.
Optionally, the heating temperature of the obtained intermediate reaction solution is 70-75 ℃.
By adopting the technical scheme, the average polymerization rate can be kept at the reaction temperature, the later polymerization rate is reduced, and the total polymerization rate is reduced due to the bitter and thresh consumption of the initiator.
Optionally, the pH is adjusted to be slightly alkaline, and the slightly alkaline pH range is 7.5-8.
By adopting the technical scheme, the pH value of the ammonia water is adjusted, so that the product cannot be influenced, and the precipitation rate of the product is higher within the range of pH 7.5-8.
Optionally, the dodecyl heptyl methacrylate, 75-80% of emulsifier and 25-30% of deionized water are stirred and mixed uniformly at the rotating speed of 500r/min to obtain the dodecyl heptyl methacrylate preparation liquid.
By adopting the technical scheme, the dodecyl heptyl methacrylate prepared solution obtained by mixing under the condition has better dispersibility, and is favorable for reaction.
Optionally, the cross-linking agent is one or more of the following groups of the ceramic SL8, SL 12, 7028 and 7560.
By adopting the technical scheme, the crosslinking agent accelerates the curing of the modified fluorine release layer.
The application provides a manufacturing method of an optical fluorine release film with a multilayer structure, which comprises the following steps:
fully dispersing, mixing and filtering the modified fluorine release agent and fluorocarbon resin to obtain main adhesive A; compounding the main adhesive A with a cross-linking agent to obtain main adhesive B; compounding the main adhesive B and a UV photoinitiator, and uniformly stirring to obtain a modified fluorine release coating 1; compounding the main adhesive B and a thermal catalyst, and uniformly stirring to obtain a modified fluorine release coating 2;
coating the modified fluorine release coating 1 on a PET substrate through a reticulate pattern coating production line, wherein the thickness of the coating is 0.05-0.1 mu m, carrying out UV light curing, coating the modified fluorine release coating 2 through the reticulate pattern coating production line again, and obtaining the optical fluorine release film with a multilayer structure after heat curing, cooling and winding, wherein the thickness of the coating is 0.03-0.07 mu m.
Through adopting above-mentioned technical scheme, adopt the mode of reticulate pattern coating to coat the multilayer fluorine from the type layer, reduced organosilicon pressure sensitive adhesive and substrate contact's possibility to, the mode of reticulate pattern coating has reduced the area of contact with organosilicon pressure sensitive adhesive, has improved the release performance from the type membrane.
Optionally, the UV light curing condition is irradiation intensity of 0.2-6 mW/cm < 2 >, and irradiation time of 500-3000 seconds.
By adopting the technical scheme, the curing is carried out under the condition, and the obtained fluorine release layer has the best curing effect.
Alternatively, the heat curing temperature is 80℃to 130 ℃.
By adopting the technical scheme, the curing is complete and takes a short time at the temperature.
In summary, the present application has the following beneficial effects:
1. the fluorine-containing polyacrylate is synthesized by using the dodecyl methacrylate and the 10-hydroxydecenoic acid as main raw materials, and the 10-hydroxydecenoic acid is used as a crosslinking monomer, so that the chain segment of the hydroxyl is longer, the connecting chain between the mutually crosslinked polymers is longer, the movement between polymer molecules is more flexible, and the toughness of the polymer is increased. The scratch resistance of the modified fluorine release layer is improved;
2. the fluorine is from type membrane in this application adopts multilayer fluorine to be from type layer through reticulation coated stack mode, through coating in proper order, solidification modified fluorine from type coating to the fluorine is from type membrane's release performance has effectively been improved.
Detailed Description
The present application is described in further detail below.
Introduction of raw materials
TABLE 1 preparation raw materials for optical fluorine release film with multilayer structure
Examples
Example 1
An optical fluorine release film with a multilayer structure comprises a PET substrate surface, a fluorine release layer 1 arranged on the PET substrate surface and a fluorine release layer 2 arranged on the fluorine release layer 1.
The fluorine release layer 1 comprises the following components in parts by weight: 30% of modified fluorine release agent, 0.2% of Dow SL8, 0.1% -3% of UV photoinitiator and the balance of polytetrafluoroethylene alkoxy resin; the fluorine release layer 2 comprises the following components: 30% of modified fluorine release agent, 0.2% of Dow SL8, 0.1% -3% of thermal catalyst and the balance of polytetrafluoroethylene alkoxy resin;
the modified fluorine release agent comprises the following preparation raw materials in parts by weight: 30% of dodecyl heptyl methacrylate, 15% of 10-hydroxydecenoic acid, 0.3% of ammonium persulfate, 0.1% of Ziegler-Natta catalyst, 1% of dodecyl mercaptan, 2% of ammonium polyoxyethylene nonylphenol ether sulfate emulsifier, 0.1% of potassium hydrogen phthalate pH buffer and the balance of deionized water;
the preparation method of the modified fluorine release agent comprises the following steps:
uniformly mixing ammonium persulfate with 25% deionized water to prepare an ammonium persulfate aqueous solution;
uniformly stirring and mixing dodecyl heptyl methacrylate, 80% of ammonium polyoxyethylene nonylphenol ether sulfate emulsifier and 25% of deionized water at a rotating speed of 500r/min to obtain dodecyl heptyl methacrylate preparation liquid; uniformly mixing 20% of dodecyl heptyl methacrylate preparation solution, 30% of ammonium persulfate aqueous solution, 25% of nonylphenol polyoxyethylene ether ammonium sulfate emulsifier, potassium hydrogen phthalate pH buffer and the rest of deionized water, and reacting at 75 ℃ for 25min to obtain an intermediate reaction solution; adding dodecyl mercaptan and Ziegler-Natta catalyst into the intermediate reaction liquid, mixing uniformly, then uniformly mixing 10-hydroxydecenoic acid and the rest of the dodecyl heptyl methacrylate preparation liquid, dripping the rest of ammonium persulfate aqueous solution into the intermediate reaction liquid while dripping the rest of ammonium persulfate aqueous solution into the intermediate reaction liquid, raising the temperature to 85 ℃, reacting for 1.5h, reducing the temperature to below 45 ℃, regulating the pH value to 7.5 by using ammonia water, filtering and discharging to obtain the modified fluorine release agent.
The manufacturing method of the optical fluorine release film with the multilayer structure comprises the following steps:
fully dispersing, mixing and filtering the modified fluorine release agent and polytetrafluoroethylene alkoxy resin to obtain main adhesive A; the main adhesive A and the ceramic SL8 are subjected to high-speed dispersion for 20min and compounded at the rotating speed of 900rpm to obtain a main adhesive B; the main adhesive B and the UV photoinitiator are subjected to high-speed dispersion for 20min at the rotating speed of 900rpm to be compounded and stirred uniformly, so that the modified fluorine release coating 1 is obtained;
the main adhesive B and the thermal catalyst are dispersed for 20min at a high speed under the rotation speed of 900rpm for compounding, and are uniformly stirred to obtain the modified fluorine release coating 2;
the modified fluorine release coating 1 is coated on a PET substrate through a reticulate pattern coating production line, the thickness of the coating is 0.05 mu m, the coating enters a UV lamp box, the curing is carried out under the conditions of the irradiation intensity of 6mW/cm < 2 > and the irradiation time of 3000 seconds, the modified fluorine release layer 1 cured by the UV lamp box is obtained, the reticulate pattern coating production line is adopted again to coat the modified fluorine release coating 2 on the modified fluorine release layer 1, the thickness of the coating is 0.03 mu m, the coating enters an oven, the curing is carried out under the temperature of 130 ℃, and the optical fluorine release film with a multilayer structure is obtained after cooling and rolling.
Example 2
An optical fluorine release film with a multilayer structure comprises a PET substrate surface, a fluorine release layer 1 arranged on the PET substrate surface and a fluorine release layer 2 arranged on the fluorine release layer 1.
The fluorine release layer 1 comprises the following components in parts by weight: 50% of modified fluorine release agent, 7560% of Dow, 0.1% -3% of UV photoinitiator and the balance of polytetrafluoroethylene alkoxy resin; the fluorine release layer 2 comprises the following components: 50% of modified fluorine release agent, 7560% of Dow 7560%, 0.1% of thermal catalyst and the balance of polytetrafluoroethylene alkoxy resin;
the modified fluorine release agent comprises the following preparation raw materials in parts by weight: 40% of dodecyl heptyl methacrylate, 10% of 10-hydroxydecenoic acid, 0.3% of ammonium persulfate, 1.5% of Ziegler-Natta catalyst, 0.1% of dodecyl mercaptan, 2.5% of polyoxyethylene nonylphenol ether emulsifier, 0.55% of potassium hydrogen phthalate pH buffer and the balance of deionized water;
the preparation method of the modified fluorine release agent comprises the following steps:
uniformly mixing ammonium persulfate with 30% deionized water to prepare an ammonium persulfate aqueous solution;
uniformly stirring and mixing the dodecyl heptyl methacrylate, 75% of a polyoxyethylene nonylphenol ether emulsifier and 30% of deionized water at a rotating speed of 500r/min to obtain a dodecyl heptyl methacrylate preparation liquid; uniformly mixing 20% of dodecyl heptyl methacrylate preparation liquid, 30% of ammonium persulfate aqueous solution, the rest of nonylphenol polyoxyethylene ether emulsifier, a potassium hydrogen phthalate pH buffer and the rest of deionized water, and reacting for 35min at the temperature of 70 ℃ to obtain an intermediate reaction liquid; adding dodecyl mercaptan and Ziegler-Natta catalyst into the intermediate reaction liquid, mixing uniformly, then uniformly mixing 10-hydroxydecenoic acid and the rest of the dodecyl heptyl methacrylate preparation liquid, dripping the rest of ammonium persulfate aqueous solution into the intermediate reaction liquid, simultaneously dripping the rest of ammonium persulfate aqueous solution into the intermediate reaction liquid, raising the temperature to 90 ℃, reacting for 1h, reducing the temperature to below 45 ℃, regulating the pH value to 8 by using ammonia water, filtering and discharging to obtain the modified fluorine release agent.
The manufacturing method of the optical fluorine release film with the multilayer structure comprises the following steps:
fully dispersing, mixing and filtering the modified fluorine release agent and polytetrafluoroethylene alkoxy resin to obtain main adhesive A; the main adhesive A and the ceramic SL8 are subjected to high-speed dispersion for 20min and compounded at the rotating speed of 900rpm to obtain a main adhesive B; the main adhesive B and the UV photoinitiator are subjected to high-speed dispersion for 20min at the rotating speed of 900rpm to be compounded and stirred uniformly, so that the modified fluorine release coating 1 is obtained;
the main adhesive B and the thermal catalyst are dispersed for 20min at a high speed under the rotation speed of 900rpm for compounding, and are uniformly stirred to obtain the modified fluorine release coating 2;
the modified fluorine release coating 1 is coated on a PET substrate through a reticulate pattern coating production line, the thickness of the coating is 0.1 mu m, the coating enters a UV lamp box, the curing is carried out under the conditions of the irradiation intensity of 0.2mW/cm < 2 >, the dose of 200mJ/cm < 2 >, and the irradiation time of 500 seconds, the modified fluorine release layer 1 cured through the UV lamp box is obtained, the reticulate pattern coating production line is adopted again to coat the modified fluorine release coating 2 on the modified fluorine release layer 1, the thickness of the coating is 0.07 mu m, the coating enters an oven, the curing is carried out under the condition of the temperature of 80 ℃, and the optical fluorine release film with a multilayer structure is obtained after cooling and winding.
Example 3
An optical fluorine release film with a multilayer structure comprises a PET substrate surface, a fluorine release layer 1 arranged on the PET substrate surface and a fluorine release layer 2 arranged on the fluorine release layer 1.
The fluorine release layer 1 comprises the following components in parts by weight: 40% of modified fluorine release agent, 75602.5% of Dow, 2.5% of Dow SL, 1.5% of UV photoinitiator and the balance of polytetrafluoroethylene alkoxy resin; the fluorine release layer 2 comprises the following components: 50% of modified fluorine release agent, 2.5% of Dow 7560, 2.5% of Dow SL, 1.5% of thermal catalyst and the balance of polytetrafluoroethylene alkoxy resin;
the modified fluorine release agent comprises the following preparation raw materials in parts by weight: 35% of dodecaheptyl methacrylate, 12.5% of 10-hydroxydecenoic acid, 0.45% of ammonium persulfate, 0.6% of Ziegler-Natta catalyst, 0.7% of dodecyl mercaptan, 2.3% of emulsifier, 0.3% of potassium hydrogen phthalate pH buffer and the balance of deionized water;
the preparation method of the modified fluorine release agent comprises the following steps:
uniformly mixing ammonium persulfate with 27% deionized water to prepare an ammonium persulfate aqueous solution;
uniformly stirring and mixing the dodecyl heptyl methacrylate, 77% of CO-436 and 23% of deionized water at a rotating speed of 500r/min to obtain a dodecyl heptyl methacrylate preparation liquid; preparing an emulsifier from a polyoxyethylene nonylphenol ether ammonium sulfate emulsifier and a polyoxyethylene nonylphenol ether emulsifier according to a ratio of 1:1; uniformly mixing 17% of dodecyl heptyl methacrylate preparation liquid, 33% of ammonium persulfate aqueous solution, 23% of emulsifier, potassium hydrogen phthalate pH buffer and the rest deionized water, and reacting at 75 ℃ for 25min to obtain intermediate reaction liquid; adding dodecyl mercaptan and Ziegler-Natta catalyst into the intermediate reaction liquid, mixing uniformly, then mixing 10-hydroxydecenoic acid and the rest of the dodecyl heptyl methacrylate preparation liquid uniformly, dripping the rest of ammonium persulfate aqueous solution into the intermediate reaction liquid, raising the temperature to 90 ℃, reacting for 1h, cooling to below 45 ℃, regulating the pH to 7.7 by using ammonia water, filtering and discharging to obtain the modified fluorine release agent.
The manufacturing method of the optical fluorine release film with the multilayer structure comprises the following steps:
fully dispersing, mixing and filtering the modified fluorine release agent and polytetrafluoroethylene alkoxy resin to obtain main adhesive A; the main adhesive A is compounded with the Dow SL8 and the Dow 7560 at a rotating speed of 900rpm for high-speed dispersion for 20min to obtain a main adhesive B; the main adhesive B and Darocur 1173 are dispersed for 20min at a high speed under the rotation speed of 900rpm for compounding and uniformly stirred to obtain the modified fluorine release coating 1;
the main adhesive B and the platinum catalyst are dispersed for 20min at a high speed under the rotation speed of 900rpm for compounding, and are uniformly stirred to obtain the modified fluorine release coating 2;
the modified fluorine release coating 1 is coated on a PET substrate through a reticulate pattern coating production line, the thickness of the coating is 0.07 mu m, the PET substrate enters a UV lamp box, the modified fluorine release coating 1 is cured under the conditions of the irradiation intensity of 3mW/cm < 2 >, the dose of 1200mJ/cm < 2 > and the irradiation time of 1700 seconds, the modified fluorine release coating 1 cured through the UV lamp box is obtained, the reticulate pattern coating production line is adopted again to coat the modified fluorine release coating 2 on the modified fluorine release coating 1, the thickness of the coating is 0.05 mu m, the modified fluorine release coating enters an oven, the modified fluorine release coating is cured at the temperature of 110 ℃, and the optical fluorine release film with a multilayer structure is obtained after cooling and winding.
Comparative example
Comparative example 1
A difference between the fluorine release film and the example 3 is that the equivalent amount of dodecyl mercaptan is replaced by Ziegler-Natta catalyst, a modified fluorine release agent is prepared according to the same steps, and a modified fluorine release layer is coated according to the same steps, so that the fluorine release film is obtained.
Comparative example 2
A difference between the fluorine release film and the example 3 is that the Ziegler-Natta catalyst is replaced by dodecyl mercaptan, a modified fluorine release agent is prepared according to the same steps, and a modified fluorine release layer is coated according to the same steps, so that the fluorine release film is obtained.
Comparative example 3
An existing fluoride release film differs from example 3 in that 10-hydroxydecenoic acid was replaced with 4-hydroxybutyl acrylate in equal amounts and no Ziegler-Natta catalyst and no dodecyl mercaptan was added. Preparing a modified fluorine release agent according to the same steps, and coating a modified fluorine release layer according to the same steps to obtain the existing fluorine release film.
Performance detection
Abrasion resistance test of fluorine release film
Referring to the method specified in GB1768-79 (89), in the test, the weight loss amount of the fluorine release film is used as an index of abrasion resistance of the fluorine release film, and the smaller the weight loss amount, the higher the abrasion resistance of the fluorine release film. The fluorine release agent 1 prepared in examples 1 to 3 and comparative examples 1 to 3 was applied to a sample plate and cured, and then the corresponding fluorine release agent 2 was applied to the surface of the fluorine release layer 1 (sample plate diameter: 200mm, center hole diameter: 9 mm), and after curing, the mixture was ground and rotated for 50 rotations. The test results are shown in Table 2.
Scratch resistance test of fluorine release agent
The fluorine release films prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to topping at a speed of 50mm/min by using a steel needle having a diameter of 1.0mm and a spherical tip radius of 0.5mm, and the scratch resistance was measured by using the minimum load value at which the needle can pierce the release film, the larger the minimum load value, the better the scratch resistance. The test results are shown in Table 3.
Release force test of fluorine release film
The release force of the fluoro release film was tested according to the method specified in GBT25256-2010, wherein the test used a four-dimensional MY2G tape.
TABLE 2 film resistance test results of the fluorine release films prepared in examples 1 to 3 and comparative examples 1 to 3
TABLE 3 scratch resistance and Release force test results of the fluorine release films prepared in examples 1 to 3 and comparative examples 1 to 3
| Sample of | Scratch resistance (N) | Release force (g/inch) | Residual Rate (%) |
| Example 1 | 16 | 3.01 | 98 |
| Example 2 | 16 | 3.22 | 96.6 |
| Example 3 | 18 | 2.87 | 97.3 |
| Comparative example 1 | 9 | 6.64 | 80.2 |
| Comparative example 2 | 9 | 6.95 | 79.8 |
| Comparative example 3 | 10 | 6.24 | 80.7 |
According to the data in tables 2 and 3, it can be seen from the data in examples 3 and 3 that the fluorine release film prepared by the method of the present application has better abrasion resistance, the scratch resistance of the existing fluorine release film is generally about 10N, and the fluorine release film prepared by the method of the present application has better scratch resistance than the existing fluorine release film.
Comparing the data of example 3 with comparative example 3 in tables 2 and 3, 4-hydroxybutyl acrylate is a commonly used anti-wear agent in the coating industry, and 10-hydroxydecenoic acid used in the present application has a better effect on improving scratch resistance of the fluorine release film than the commonly used anti-wear agent. The modified fluorine-containing acrylic ester prepared by reacting 10-hydroxydecenoic acid with dodecyl methyl methacrylate under the action of Ziegler-Natta catalyst and dodecyl mercaptan has long connecting chain segment, long connecting chain between cross-linked polymers and flexible movement between polymer molecules, so that the toughness of the polymer is increased. When the external force is applied, the deformation of the molecular chain network can be recovered in time, so that the scratch resistance of the modified fluorine release layer is improved.
Comparing the data of example 3 with comparative example 1 and comparative example 2 in table 3, the prepared fluorocarbon release film was weak in scratch resistance and large in release force when using Ziegler-Natta catalyst alone or dodecyl mercaptan alone. It is described that the polymerization of 10-hydroxydecenoic acid with dodecaheptyl methacrylate can be promoted only when a Ziegler-Natta catalyst is used in combination with dodecyl mercaptan, thereby improving the scratch resistance of the modified fluorine release agent. In addition, the dodecyl mercaptan can reduce the occurrence of chain transfer reaction, so that the cross-linking positions of the fluorine-containing polyacrylic acid are uniformly distributed, the surface energy of the fluorine release layer is further reduced in a more compact and orderly manner, and the release force of the fluorine release film is reduced.
The above-described embodiments are merely illustrative of the present application and are not intended to limit the present application, and those skilled in the art, after having read the present specification, may make modifications to the present application without creative contribution as required, but all are intended to be within the protection scope of the present application.
Claims (9)
1. An optical fluorine release film with a multilayer structure, which is characterized in that: including PET substrate and the fluorine that sets up on PET substrate surface from type layer 1 and fluorine from type layer 2 that sets up on 1, according to parts by weight, fluorine is from type layer 1 including following component: 30-50% of modified fluorine release agent, 0.2-5% of cross-linking agent, 0.1-3% of UV photoinitiator and the balance of fluorocarbon resin; the fluorine release layer 2 comprises the following components: 30-50% of modified fluorine release agent, 0.2-5% of cross-linking agent, 0.1-3% of thermal catalyst and the balance of fluorocarbon resin;
the modified fluorine release agent comprises the following preparation raw materials in parts by weight: 30-40% of dodecaheptyl methacrylate, 10-15% of 10-hydroxydecenoic acid, 0.3-0.6% of ammonium persulfate, 0.1-1.5% of Ziegler-Natta catalyst, 0.1-1% of dodecyl mercaptan, 2-2.5% of emulsifier, 0.1-0.55% of standard pH buffering agent and the balance of deionized water;
the preparation method of the modified fluorine release agent comprises the following steps: uniformly mixing ammonium persulfate with 25% -30% deionized water to prepare an ammonium persulfate aqueous solution; uniformly mixing dodecyl heptyl methacrylate, 75-80% of an emulsifier and 25-30% of deionized water to obtain dodecyl heptyl methacrylate preparation liquid; uniformly mixing 15% -20% of dodecyl heptyl methacrylate preparation liquid, 30% -35% of ammonium persulfate aqueous solution, the rest of emulsifying agent, standard pH buffering agent and the rest of deionized water, and heating for reaction for 25-35 min to obtain intermediate reaction liquid; adding dodecyl mercaptan and Ziegler-Natta catalyst into the intermediate reaction liquid, mixing uniformly, then uniformly mixing 10-hydroxydecenoic acid and the rest of the dodecyl heptyl methacrylate preparation liquid, dripping the rest of ammonium persulfate aqueous solution into the intermediate reaction liquid, reacting for 1-1.5 h at the temperature of 85-90 ℃, cooling to below 45 ℃, regulating the pH value to be alkalescent, filtering and discharging to obtain the modified fluorine release agent.
2. The optical fluoride release film having a multilayer structure according to claim 1, wherein: the emulsifier is one or more of polyoxyethylene nonylphenol ether ammonium sulfate emulsifier and polyoxyethylene nonylphenol ether emulsifier.
3. The optical fluoride release film having a multilayer structure according to claim 1, wherein: the heating temperature of the obtained intermediate reaction liquid is 70-75 ℃.
4. The optical fluoride release film having a multilayer structure according to claim 1, wherein: the pH value is adjusted to be alkalescent, and the alkalescent pH value is 7.5-8.
5. The optical fluoride release film having a multilayer structure according to claim 1, wherein: the dodecyl heptyl methacrylate, 75-80% of emulsifier and 25-30% of deionized water are stirred and mixed uniformly at the rotating speed of 500r/min to obtain the dodecyl heptyl methacrylate preparation liquid.
6. The optical fluoride release film having a multilayer structure according to claim 1, wherein: the cross-linking agent is one or more of the following ceramic SL8, SL 12, 7028 and 7560.
7. A method for producing an optical fluorine release film having a multilayer structure according to any one of claims 1 to 6, characterized by comprising: the method comprises the following steps:
fully dispersing, mixing and filtering the modified fluorine release agent and fluorocarbon resin to obtain main adhesive A; compounding the main adhesive A with a cross-linking agent to obtain main adhesive B; compounding the main adhesive B and a UV photoinitiator, and uniformly stirring to obtain a modified fluorine release coating 1;
compounding the main adhesive B and a thermal catalyst, and uniformly stirring to obtain a modified fluorine release coating 2;
coating the modified fluorine release coating 1 on a PET substrate through a reticulate pattern coating production line, wherein the thickness of the coating is 0.05-0.1 mu m, carrying out UV light curing, coating the modified fluorine release coating 2 through the reticulate pattern coating production line again, and obtaining the optical fluorine release film with a multilayer structure after heat curing, cooling and winding, wherein the thickness of the coating is 0.03-0.07 mu m.
8. The method for producing an optical fluorine release film having a multilayer structure according to claim 7, wherein: the UV light curing condition is the irradiation intensity of 0.2-6 mW/cm < 2 >, and the irradiation time of 500-3000 seconds.
9. The method for producing an optical fluorine release film having a multilayer structure according to claim 7, wherein: the heat curing temperature is 80-130 ℃.
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| CN116023836A (en) * | 2023-02-09 | 2023-04-28 | 安徽省林田光电科技有限公司 | Synthesis method of aqueous fluorine release agent and application of aqueous fluorine release agent in PET film |
| CN116284925A (en) * | 2023-02-09 | 2023-06-23 | 安徽省林田光电科技有限公司 | PET film material containing aqueous fluorine release agent and synthesis process thereof |
| CN116640344A (en) * | 2023-05-09 | 2023-08-25 | 太湖金张科技股份有限公司 | Fluorine release film with extremely low release force and wide application range |
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