CN116285730B - High-weather-resistance self-cleaning reflective film and preparation method thereof - Google Patents

High-weather-resistance self-cleaning reflective film and preparation method thereof Download PDF

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CN116285730B
CN116285730B CN202310124147.0A CN202310124147A CN116285730B CN 116285730 B CN116285730 B CN 116285730B CN 202310124147 A CN202310124147 A CN 202310124147A CN 116285730 B CN116285730 B CN 116285730B
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curing
monomer
reflective film
sensitive adhesive
film
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CN116285730A (en
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潘晶
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Hubei Prism New Material Technology Co ltd
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Hubei Prism New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
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    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/003—Presence of polysiloxane in the primer coating
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  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The application relates to the technical field of reflective films, in particular to a high weather-resistant self-cleaning reflective film and a preparation method thereof. Firstly, carrying out two-sided corona treatment on a polyester film, coating a photo-curing adhesive on one side of the polyester film, extruding by using a mold roller, and then photo-curing to form a prism microstructure, wherein a reflecting layer is processed by adopting vacuum evaporation, then, compounding and mixing fluorine-containing siloxane monomer, pentaerythritol tetra-3-mercaptopropionate, vinyl-terminated polydimethylsiloxane and a photoinitiator to form a protective solution, and then, immersing the processed polyester film in the protective solution for ultraviolet curing, so that a protective layer is formed on the surface of the reflecting layer by curing; and coating a pressure-sensitive adhesive on the back of the polyester film, and sticking a release film to obtain a reflective film product. The reflective film prepared by the application has excellent self-cleaning performance, improved water resistance and excellent weather resistance, can be used as traffic sign, and can still maintain excellent adhesive performance when a plurality of layers of reflective films are compounded.

Description

High-weather-resistance self-cleaning reflective film and preparation method thereof
Technical Field
The application relates to the technical field of reflective films, in particular to a high weather-resistant self-cleaning reflective film and a preparation method thereof.
Background
The reflective film is a retroreflective material which can be directly applied to the film, and is generally applied to road traffic signs, car body reflective signs, reflective advertising materials, outdoor facility indication signs, equipment, pipeline reflective signs and the like; the reflective film used at present mainly can be divided into two major categories, namely a microprism structure and a glass microsphere structure, PMMA, PET or PVC is generally adopted as a surface protection layer when the reflective film is manufactured, but the hydrolysis resistance is poor, and the overall weather resistance can not meet the actual requirements, so that the adoption of a fluorine-containing material as a surface layer gradually becomes the mainstream choice of people.
In addition, when the reflective film is used as a traffic sign, two layers of reflective films can be compounded sometimes, for example, traffic signs on highways are usually green-background white characters, namely, the green reflective film is used as a bottom film, the white reflective film is used as a character film, and when a fluorine material is used as a surface protection layer, the character film is easy to be stuck, and the practicability is poor.
Based on the above, the application discloses a highly weather-resistant self-cleaning reflective film and a preparation method thereof, which can ensure the stain resistance and water resistance of a surface protection layer, and the prepared reflective film can be suitable for the situation of multi-layer compounding so as to solve the existing technical problems.
Disclosure of Invention
The application aims to provide a high weather-resistant self-cleaning reflective film and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the application provides the following technical scheme:
a preparation method of a high weather-resistant self-cleaning reflective film comprises the following steps:
(1) Coating a photo-curing adhesive on one surface of the polyester film after corona treatment, extruding by a die roller, performing ultraviolet curing to form a prism microstructure, and then evaporating a reflecting layer on the surface of the prism microstructure;
(2) Mixing fluorine-containing siloxane monomer, pentaerythritol tetra-3-mercaptopropionate and vinyl-terminated polydimethylsiloxane, adding a photoinitiator, stirring uniformly, and stirring and dissolving dichloromethane to obtain a protection solution.
And (3) immersing the polyester film treated in the step (1) in a protective liquid, and curing for 50-60 min under ultraviolet light to form a protective layer.
In a more optimized scheme, in the step (2), the molar ratio of the fluorine-containing siloxane monomer, pentaerythritol tetra-3-mercaptopropionate and vinyl-terminated polydimethylsiloxane is 1:1: (3-4); the photoinitiator is used in an amount of 2.5 to 3wt% of the vinyl-terminated polydimethylsiloxane. The photoinitiator is 2-hydroxy-2-methyl propiophenone.
(3) And (3) coating a pressure-sensitive adhesive on one surface of the polyester film, which is far away from the reflecting layer, of the polyester film treated in the step (2), coating a release film on the surface of the pressure-sensitive adhesive, curing under ultraviolet light, and cutting to obtain a finished product. The thickness of the pressure sensitive adhesive coating is 20-30 mu m.
In the step (3), the ultraviolet curing time is 5-10 s, and the illumination intensity of the ultraviolet is 350-400 mW/cm 2 。
In a more optimized scheme, in the step (2), the preparation steps of the fluorine-containing siloxane monomer are as follows:
s1: and (3) uniformly stirring methanol and hydrochloric acid in an oil bath at the temperature of 85-90 ℃, adding gamma-mercaptopropyl trimethoxy silane, stirring and reacting for 70-75 hours, standing after the reaction is finished, separating supernatant, neutralizing the pH of the lower layer by using methanol, removing the methanol by rotary evaporation and concentration, and purifying to obtain the mercapto POSS monomer.
S2: mixing mercapto POSS monomer, perfluorobutyl ethylene and photoinitiator, stirring and dissolving dichloromethane, and stirring and reacting for 40-50 min under ultraviolet light to obtain fluorine-containing siloxane monomer.
In the more optimized scheme, in the step S1, the mass ratio of the methanol to the hydrochloric acid to the gamma-mercaptopropyl trimethoxysilane is (15-15.2): (6.4-6.6): 1, a step of; in the step S2, the molar ratio of the mercapto POSS monomer to the perfluorobutyl ethylene is 1: (3-3.1); the dosage of the photoinitiator is 1.5 to 2.5 weight percent of the total mass of the mercapto POSS monomer and the perfluorobutyl ethylene.
The preparation method of the pressure-sensitive adhesive comprises the following steps of: taking butyl acrylate, 2-ethylhexyl acrylate, acrylic acid, hydroxyethyl methacrylate, methyl methacrylate, mercapto POSS monomer and TPO, mixing and stirring uniformly, and curing for 10-15 min under ultraviolet light to obtain an acrylic ester prepolymer;
TPO and trimethylolpropane triacrylate are added into the acrylate prepolymer and stirred uniformly to obtain the pressure-sensitive adhesive. The dosage of the trimethylolpropane triacrylate is 0.8-1.5 wt% of the acrylate prepolymer, and the dosage of the TPO is 1.6-2.2 wt% of the acrylate prepolymer.
In a more optimized scheme, when the acrylate prepolymer is polymerized, the content of each reaction monomer is as follows: 20-25 parts of butyl acrylate, 70-75 parts of 2-ethylhexyl acrylate, 3-5 parts of acrylic acid, 2-4 parts of hydroxyethyl methacrylate, 5-6 parts of methyl methacrylate and 3-5 parts of mercapto POSS monomer; the TPO dosage is reversed0.5 to 1 weight percent of the total monomer; the illumination intensity of the ultraviolet light is 550-600 mW/cm 2 。
According to an optimized scheme, the reflective film is prepared by the preparation method of the high-weather-resistance self-cleaning reflective film.
Compared with the prior art, the application has the following beneficial effects:
the application discloses a high weather-resistant self-cleaning reflective film and a preparation method thereof, wherein the reflective film comprises the following components in detail from top to bottom: protective layer-reflecting layer-prism microstructure-polyester film-pressure sensitive adhesive-release film; when the scheme is implemented, the polyester film is firstly subjected to two-sided corona treatment, the polyester film is generally made of PET film, and the thickness is 50-80 mu m; coating a photo-curing adhesive on one surface of the polyester film, wherein the photo-curing adhesive comprises, but is not limited to, polyacrylate, polyurethane acrylic ester or polyepoxy acrylic ester, and the like, and is photo-cured after being extruded by a die roller to form a prism microstructure, the height of the prism microstructure is 14-18 mu m, and the period of the prism microstructure is 50-60 mu m; the specific prism angle and the structural design can be adjusted according to actual requirements; the reflecting layer is processed by vacuum evaporation, and materials include but are not limited to aluminum, silver, nickel and the like.
After vacuum evaporation of the reflecting layer, in order to protect the surface of the reflecting layer, the scheme utilizes fluorine-containing siloxane monomer, pentaerythritol tetra-3-mercaptopropionate, vinyl-terminated polydimethylsiloxane and photoinitiator to compound and mix to form a protective solution, and then the polyester film after processing is immersed in the protective solution for ultraviolet curing, so that a protective layer is formed on the surface of the reflecting layer by curing; here, it is to be explained that: when the surface of the reflective film is processed with the protective layer, the protective layer is commonly subjected to coextrusion compounding, or a wet coating is adopted to coat the protective solution on the surface of the reflective layer for curing, but the polyester film is immersed in the protective solution for curing, so that on one hand, the protective solution can protect the reflective layer, and after the fluorine-containing siloxane monomer, pentaerythritol tetra-3-mercaptopropionate and vinyl-terminated polydimethylsiloxane are combined and compounded, the surface of the reflective film can realize hydrophobic self-cleaning, and the weather resistance of the reflective film is improved; on the other hand, the protective solution is pre-primed on the other unprocessed surface of the polyester film, and as the protective solution contains a plurality of groups such as vinyl, mercapto and the like, unreacted vinyl and mercapto on the surface of the polyester film can participate in the curing reaction of the pressure-sensitive adhesive in the subsequent coating and curing process of the pressure-sensitive adhesive, thereby improving the bonding performance between the pressure-sensitive adhesive and the polyester film; meanwhile, the water resistance of the whole reflective film is greatly improved due to the impregnation treatment of the protective liquid.
In addition, the scheme adjusts the compound components of the protective solution, and in the implementation, gamma-mercaptopropyl trimethoxy silane is firstly utilized to catalyze hydrolysis and condensation to form an octamercapto POSS monomer, then mercapto and vinyl click reaction is utilized to graft perfluorobutyl ethylene onto the POSS monomer, and fluorine is introduced to obtain a fluorine-containing siloxane monomer; the scheme defines that the molar ratio of the mercapto POSS monomer to the perfluorobutyl ethylene is 1: (3-3.1) ", under the parameter condition, the monomer contains a large amount of unreacted sulfhydryl groups so as to ensure that the monomer can participate in system crosslinking subsequently.
Then, the pressure-sensitive adhesive is coated on the other surface of the polyester film, namely the surface which is not processed by the reflecting layer, and the pressure-sensitive adhesive must be limited to be an acrylic ester system pressure-sensitive adhesive containing double bonds when the scheme is designed, and the technical problem required by the scheme is that two reflecting films are sometimes compounded when the reflecting film is actually applied, one reflecting film is used as a bottom film, the other reflecting film is coated on the bottom film as a character film, in order to reduce the influence of a protective layer on the adhesiveness between the two reflecting films and avoid the adhesion of the character film, the scheme not only controls the dosage proportion of the protective layer, namely the molar ratio of fluorine-containing siloxane monomer, pentaerythritol tetra-3-mercaptopropionate and vinyl-terminated polydimethylsiloxane to be 1:1: (3-4) ", so that residual sulfhydryl groups still remain unreacted after the protective layer is cured, and when the two subsequent reflective films are compounded, the sulfhydryl groups can participate in the curing reaction under the action of ultraviolet light after the acrylate pressure-sensitive adhesive containing double bonds on the upper layer is contacted with the lower protective layer, so that the adhesive property between the two reflective films can be ensured.
Based on the conception, the scheme adjusts the component proportion of the pressure-sensitive adhesive, and the pressure-sensitive adhesive is prepared by polymerizing 20-25 parts of butyl acrylate, 70-75 parts of acrylic acid-2-ethylhexyl ester, 3-5 parts of acrylic acid, 2-4 parts of hydroxyethyl methacrylate, 5-6 parts of methyl methacrylate and 3-5 mercapto POSS monomers, coating a release film and cutting to obtain the finished product of the reflecting film.
The application discloses a high weather-resistant self-cleaning reflective film and a preparation method thereof, wherein the composition ratio of each component is proper, the hierarchical compounding process is reasonable, the prepared reflective film not only has excellent self-cleaning performance, but also has the advantages of improved water resistance and excellent weather resistance, can be used as a traffic sign, can still maintain excellent adhesive property when being compounded by a plurality of layers of reflective films, and has higher practicability.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In this example, vinyl-terminated polydimethylsiloxane (V304361), pentaerythritol tetra-3-mercaptopropionate (P463020), 2-hydroxy-2-methylpropionophenone (H110280), and the photoinitiator TPO (T107643) were all purchased from Shanghai Ala-dine. The polyester film is a PET film.
Example 1:
a preparation method of a high weather-resistant self-cleaning reflective film comprises the following steps:
(1) Coating a photo-curing adhesive on one surface of the PET film after corona treatment, extruding by a die roller, and performing ultraviolet curing to form a prism microstructure, and then evaporating a reflecting layer on the surface of the prism microstructure; the thickness of the PET film is 65 mu m, the height of the formed prism microstructure is 16 mu m, and the period of the prism microstructure is 50 mu m; the reflecting layer is aluminum and is processed by vacuum evaporation, and the thickness is 70nm.
(2) Mixing 0.5mmol of fluorine-containing siloxane monomer, 0.5mmol of pentaerythritol tetra-3-mercaptopropionate and 1.5mmol of vinyl-terminated polydimethylsiloxane, adding a photoinitiator, stirring uniformly, wherein the photoinitiator is 2-hydroxy-2-methyl propiophenone, the dosage of the photoinitiator is 2.5wt% of that of the vinyl-terminated polydimethylsiloxane, and adding 120g of dichloromethane, stirring and dissolving to obtain a protection solution.
And (3) immersing the PET film treated in the step (1) in a protective liquid, and curing for 50min under ultraviolet light to form a protective layer.
Wherein the preparation steps of the fluorine-containing siloxane monomer are as follows:
s1: 593.4g of methanol and 255.5g of hydrochloric acid are taken, evenly stirred in an oil bath at the temperature of 85 ℃, 39.3g of gamma-mercaptopropyl trimethoxy silane is added, stirred and reacted for 70 hours, the mixture is stood after the reaction is finished, the supernatant is separated, the pH of the lower layer is neutralized by methanol, the methanol is removed by rotary evaporation and concentration, and the thiol POSS monomer is obtained after purification.
S2: mixing 0.5mmol of mercapto POSS monomer, 1.5mmol of perfluorobutyl ethylene and a photoinitiator, stirring and dissolving 100g of methylene dichloride, and stirring and reacting for 40min under ultraviolet light to obtain the fluorine-containing siloxane monomer. The photoinitiator is 2-hydroxy-2-methyl propiophenone, and the dosage is 1.5 weight percent of the total mass of the mercapto POSS monomer and the perfluorobutyl ethylene.
(3) Coating a pressure-sensitive adhesive on one surface of the PET film far away from the reflecting layer, coating a release film on the surface of the pressure-sensitive adhesive, curing for 10s under ultraviolet light, wherein the illumination intensity of the ultraviolet light is 400mW/cm 2 Cutting to obtain the final product. The pressure sensitive adhesive coating thickness was 25 μm.
The pressure-sensitive adhesive comprises the following preparation steps: taking 20 parts of butyl acrylate, 75 parts of 2-ethylhexyl acrylate, 3 parts of acrylic acid, 4 parts of hydroxyethyl methacrylate, 5 parts of methyl methacrylate, 5 parts of sulfhydryl POSS monomer and TPO (thermoplastic elastomer), wherein the dosage of TPO is 0.5wt% of the total amount of the reaction monomers, mixing and stirring uniformly, curing for 10min under ultraviolet light, and the illumination intensity of the ultraviolet light is 550mW/cm 2 Obtaining the acrylic ester prepolymer.
TPO and trimethylolpropane triacrylate are added into the acrylate prepolymer and stirred uniformly to obtain the pressure-sensitive adhesive. The trimethylolpropane triacrylate was used in an amount of 1.2wt% of the acrylate prepolymer and the TPO was used in an amount of 1.8wt% of the acrylate prepolymer.
Example 2:
a preparation method of a high weather-resistant self-cleaning reflective film comprises the following steps:
(1) Coating a photo-curing adhesive on one surface of the PET film after corona treatment, extruding by a die roller, and performing ultraviolet curing to form a prism microstructure, and then evaporating a reflecting layer on the surface of the prism microstructure; the thickness of the PET film is 65 mu m, the height of the formed prism microstructure is 16 mu m, and the period of the prism microstructure is 50 mu m; the reflecting layer is aluminum and is processed by vacuum evaporation, and the thickness is 70nm.
(2) Mixing 0.5mmol of fluorine-containing siloxane monomer, 0.5mmol of pentaerythritol tetra-3-mercaptopropionate and 1.5mmol of vinyl-terminated polydimethylsiloxane, adding a photoinitiator, stirring uniformly, wherein the photoinitiator is 2-hydroxy-2-methyl propiophenone, the dosage of the photoinitiator is 2.5wt% of that of the vinyl-terminated polydimethylsiloxane, and adding 120g of dichloromethane, stirring and dissolving to obtain a protection solution.
And (3) immersing the PET film treated in the step (1) in a protective liquid, and curing for 55min under ultraviolet light to form a protective layer.
Wherein the preparation steps of the fluorine-containing siloxane monomer are as follows:
s1: 593.4g of methanol and 255.5g of hydrochloric acid are taken and stirred uniformly in an oil bath at 90 ℃, 39.3g of gamma-mercaptopropyl trimethoxy silane is added, the mixture is stirred and reacted for 72 hours, the mixture is left stand after the reaction is finished, the supernatant is separated, the pH of the lower layer is neutralized by the methanol, the methanol is removed by rotary evaporation and concentration, and the thiol POSS monomer is obtained after purification.
S2: mixing 0.5mmol of mercapto POSS monomer, 1.5mmol of perfluorobutyl ethylene and a photoinitiator, stirring and dissolving 100g of methylene dichloride, and stirring and reacting for 45min under ultraviolet light to obtain the fluorine-containing siloxane monomer. The photoinitiator is 2-hydroxy-2-methyl propiophenone, and the dosage is 1.5 weight percent of the total mass of the mercapto POSS monomer and the perfluorobutyl ethylene.
(3) Coating a pressure-sensitive adhesive on one surface of the PET film far away from the reflecting layer, coating a release film on the surface of the pressure-sensitive adhesive, curing for 10s under ultraviolet light, wherein the illumination intensity of the ultraviolet light is 400mWcm 2 Cutting to obtain the final product. The pressure sensitive adhesive coating thickness was 25 μm.
The pressure-sensitive adhesive comprises the following preparation steps: taking 24 parts of butyl acrylate, 72 parts of 2-ethylhexyl acrylate, 4 parts of acrylic acid, 3 parts of hydroxyethyl methacrylate, 5 parts of methyl methacrylate, 5 parts of sulfhydryl POSS monomer and TPO (thermoplastic elastomer), wherein the dosage of TPO is 0.5wt% of the total amount of the reaction monomers, mixing and stirring uniformly, curing for 10min under ultraviolet light, and the illumination intensity of the ultraviolet light is 550mW/cm 2 Obtaining the acrylic ester prepolymer.
TPO and trimethylolpropane triacrylate are added into the acrylate prepolymer and stirred uniformly to obtain the pressure-sensitive adhesive. The trimethylolpropane triacrylate was used in an amount of 1.2wt% of the acrylate prepolymer and the TPO was used in an amount of 1.8wt% of the acrylate prepolymer.
Example 3:
a preparation method of a high weather-resistant self-cleaning reflective film comprises the following steps:
(1) Coating a photo-curing adhesive on one surface of the PET film after corona treatment, extruding by a die roller, and performing ultraviolet curing to form a prism microstructure, and then evaporating a reflecting layer on the surface of the prism microstructure; the thickness of the PET film is 65 mu m, the height of the formed prism microstructure is 16 mu m, and the period of the prism microstructure is 50 mu m; the reflecting layer is aluminum and is processed by vacuum evaporation, and the thickness is 70nm.
(2) Mixing 0.5mmol of fluorine-containing siloxane monomer, 0.5mmol of pentaerythritol tetra-3-mercaptopropionate and 1.5mmol of vinyl-terminated polydimethylsiloxane, adding a photoinitiator, stirring uniformly, wherein the photoinitiator is 2-hydroxy-2-methyl propiophenone, the dosage of the photoinitiator is 2.5wt% of that of the vinyl-terminated polydimethylsiloxane, and adding 120g of dichloromethane, stirring and dissolving to obtain a protection solution.
And (3) immersing the PET film treated in the step (1) in a protective liquid, and curing for 60min under ultraviolet light to form a protective layer.
Wherein the preparation steps of the fluorine-containing siloxane monomer are as follows:
s1: 593.4g of methanol and 255.5g of hydrochloric acid are taken and stirred uniformly in an oil bath at 90 ℃, 39.3g of gamma-mercaptopropyl trimethoxy silane is added, the mixture is stirred and reacted for 75 hours, the mixture is left stand after the reaction is finished, the supernatant is separated, the pH of the lower layer is neutralized by the methanol, the methanol is removed by rotary evaporation and concentration, and the thiol POSS monomer is obtained after purification.
S2: mixing 0.5mmol of mercapto POSS monomer, 1.5mmol of perfluorobutyl ethylene and a photoinitiator, stirring and dissolving 100g of methylene dichloride, and stirring and reacting for 50min under ultraviolet light to obtain the fluorine-containing siloxane monomer. The photoinitiator is 2-hydroxy-2-methyl propiophenone, and the dosage is 1.5 weight percent of the total mass of the mercapto POSS monomer and the perfluorobutyl ethylene.
(3) Coating a pressure-sensitive adhesive on one surface of the PET film far away from the reflecting layer, coating a release film on the surface of the pressure-sensitive adhesive, curing for 10s under ultraviolet light, wherein the illumination intensity of the ultraviolet light is 400mW/cm 2 Cutting to obtain the final product. The pressure sensitive adhesive coating thickness was 25 μm.
The pressure-sensitive adhesive comprises the following preparation steps: taking 25 parts of butyl acrylate, 70 parts of 2-ethylhexyl acrylate, 5 parts of acrylic acid, 2 parts of hydroxyethyl methacrylate, 6 parts of methyl methacrylate, 5 parts of sulfhydryl POSS monomer and TPO (thermoplastic elastomer), wherein the dosage of TPO is 0.5wt% of the total amount of the reaction monomers, mixing and stirring uniformly, curing for 10min under ultraviolet light, and the illumination intensity of the ultraviolet light is 550mW/cm 2 Obtaining the acrylic ester prepolymer.
TPO and trimethylolpropane triacrylate are added into the acrylate prepolymer and stirred uniformly to obtain the pressure-sensitive adhesive. The trimethylolpropane triacrylate was used in an amount of 1.2wt% of the acrylate prepolymer and the TPO was used in an amount of 1.8wt% of the acrylate prepolymer.
Comparative example 1:
comparative example 1 experiments were conducted with example 2 as a control group, in which no mercapto POSS monomer was added to the pressure sensitive adhesive of comparative example 1, and the remaining process steps were identical to example 2, with the specific adjustment steps:
the pressure-sensitive adhesive comprises the following preparation steps: taking 24 parts of butyl acrylate, 72 parts of 2-ethylhexyl acrylate, 4 parts of acrylic acid, 3 parts of hydroxyethyl methacrylate, 5 parts of methyl methacrylate and TPO (thermoplastic elastomer), wherein the TPO is the total amount of all the reaction monomers0.5wt percent, evenly mixing and stirring, curing for 10min under ultraviolet light, wherein the illumination intensity of the ultraviolet light is 550mW/cm 2 Obtaining the acrylic ester prepolymer.
TPO and trimethylolpropane triacrylate are added into the acrylate prepolymer and stirred uniformly to obtain the pressure-sensitive adhesive. The trimethylolpropane triacrylate was used in an amount of 1.2wt% of the acrylate prepolymer and the TPO was used in an amount of 1.8wt% of the acrylate prepolymer.
Comparative example 2:
comparative example 2 experiments were carried out with example 2 as a control group, the protective liquid of comparative example 2 was not introduced with fluorosilicone monomers, and the rest of the process steps were the same as in example 2, with the following specific adjustment steps:
(2) 1.0mmol of pentaerythritol tetra-3-mercaptopropionate and 1.5mmol of vinyl-terminated polydimethylsiloxane are mixed, a photoinitiator is added and stirred uniformly, the photoinitiator is 2-hydroxy-2-methyl propiophenone, the amount of the photoinitiator is 2.5wt% of the vinyl-terminated polydimethylsiloxane, and 120g of methylene dichloride is added and stirred and dissolved to obtain the protection liquid.
And (3) immersing the PET film treated in the step (1) in a protective liquid, and curing for 55min under ultraviolet light to form a protective layer.
Comparative example 3:
comparative example 3 experiments were carried out with comparative example 2 as control, the amounts of pentaerythritol tetra-3-mercaptopropionate and vinyl-terminated polydimethylsiloxane were adjusted in comparative example 3, the remaining process steps being identical to example 2, the specific adjustment steps being:
(2) Mixing 0.5mmol of pentaerythritol tetra-3-mercaptopropionate and 1.5mmol of vinyl-terminated polydimethylsiloxane, adding a photoinitiator, stirring uniformly, wherein the photoinitiator is 2-hydroxy-2-methyl propiophenone, the dosage of the photoinitiator is 2.5wt% of the vinyl-terminated polydimethylsiloxane, and adding 120g of dichloromethane, stirring and dissolving to obtain the protection liquid.
And (3) immersing the PET film treated in the step (1) in a protective liquid, and curing for 55min under ultraviolet light to form a protective layer.
Detection experiment:
1. the reflective films prepared in examples 1-3 and comparative examples 1-3 were tested for the surface water contact angle of the protective layer, the water drop size was 5. Mu.L, and the same sample was tested for different positions and averaged 3-5 times.
2. Taking 2 reflective films prepared in examples 1-3 and comparative examples 1-3, peeling off a release film of one reflective film, bonding the release film on a protective layer of the other reflective film, compacting by a compression roller, and irradiating for 10min under ultraviolet light to obtain a test sample; referring to the detection method 2 disclosed in GB/T2792-2014, one end of the lower reflective film is fixed in a clamp during the test, the upper reflective film is peeled at 180 degrees, and the peeling strength is recorded.
Project Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3
Contact angle of water 154° 155° 154° 155° 137° 152°
Peel strength N× (24 mm) -1 15.2 15.4 15.3 14.5 14.9 14.2
Conclusion: as can be seen from the above table data, in comparative example 1, when the mercapto POSS monomer is not added to the pressure-sensitive adhesive, the surface hydrophobicity of the protective layer has little influence, but can have influence on the adhesion property of the pressure-sensitive adhesive, and when the two reflective films are compounded, the peel strength is reduced; in comparative example 2, the fluorine-containing siloxane monomer is not introduced into the protective liquid, so that the amount of pentaerythritol tetra-3-mercaptopropionate needs to be increased to ensure the adhesion between two subsequent reflective films, but the water contact angle of the protective layer is greatly reduced, and the peeling strength is also reduced, but the reduction range is smaller; in comparative example 3, in order to ensure that the water contact angle of the protective layer is greater than 150 °, the ratio of pentaerythritol tetra-3-mercaptopropionate to vinyl-terminated polydimethylsiloxane was adjusted, and the amount of pentaerythritol tetra-3-mercaptopropionate was reduced, but it resulted in a significant decrease in peel strength.
The method has the advantages that the composition ratio of each component is proper, the hierarchical compounding process is reasonable, the prepared reflective film has excellent self-cleaning performance, the water resistance of the reflective film is improved, the weather resistance is excellent, the reflective film can be used as a traffic sign, the excellent adhesive performance can be kept when the multi-layer reflective film is compounded, and the practicability is higher.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (4)

1. A preparation method of a highly weather-resistant self-cleaning reflective film is characterized by comprising the following steps: the method comprises the following steps:
(1) Coating a photo-curing adhesive on one surface of the polyester film after corona treatment, extruding by a die roller, performing ultraviolet curing to form a prism microstructure, and then evaporating a reflecting layer on the surface of the prism microstructure;
(2) Mixing fluorine-containing siloxane monomer, pentaerythritol tetra-3-mercaptopropionate and vinyl-terminated polydimethylsiloxane, adding a photoinitiator, stirring uniformly, and stirring and dissolving dichloromethane to obtain a protection solution; the molar ratio of the fluorine-containing siloxane monomer to pentaerythritol tetra-3-mercaptopropionate to vinyl-terminated polydimethylsiloxane is 1:1: (3-4); the photoinitiator is 2.5-3 wt% of vinyl-terminated polydimethylsiloxane;
soaking the polyester film treated in the step (1) in a protective liquid, and curing for 50-60 min under ultraviolet light to form a protective layer;
the preparation method of the fluorine-containing siloxane monomer comprises the following steps:
s1: taking methanol and hydrochloric acid, stirring uniformly in an oil bath at 85-90 ℃, adding gamma-mercaptopropyl trimethoxy silane, stirring and reacting for 70-75 hours, standing after the reaction is finished, separating supernatant, neutralizing the pH of the lower layer by using methanol, removing the methanol by rotary evaporation and concentration, and purifying to obtain a mercapto POSS monomer;
s2: mixing a sulfhydryl POSS monomer, perfluorobutyl ethylene and a photoinitiator, stirring and dissolving methylene dichloride, and stirring and reacting for 40-50 min under ultraviolet light to obtain a fluorine-containing siloxane monomer;
in the step S1, the mass ratio of the methanol to the hydrochloric acid to the gamma-mercaptopropyl trimethoxysilane is (15-15.2): (6.4-6.6): 1, a step of; in the step S2, the molar ratio of the mercapto POSS monomer to the perfluorobutyl ethylene is 1: (3-3.1); the dosage of the photoinitiator is 1.5 to 2.5 weight percent of the total mass of the mercapto POSS monomer and the perfluorobutyl ethylene;
(3) Coating a pressure-sensitive adhesive on one surface of the polyester film, far away from the reflecting layer, of the polyester film treated in the step (2), coating a release film on the surface of the pressure-sensitive adhesive, curing under ultraviolet light, and cutting to obtain a finished product;
the pressure-sensitive adhesive comprises the following preparation steps: taking butyl acrylate, 2-ethylhexyl acrylate, acrylic acid, hydroxyethyl methacrylate, methyl methacrylate, mercapto POSS monomer and TPO, mixing and stirring uniformly, and curing for 10-15 min under ultraviolet light to obtain an acrylic ester prepolymer; TPO and trimethylolpropane triacrylate are added into the acrylate prepolymer and stirred uniformly to obtain a pressure-sensitive adhesive; when the acrylic ester prepolymer is polymerized, the content of each reaction monomer is as follows: 20-25 parts of butyl acrylate, 70-75 parts of 2-ethylhexyl acrylate, 3-5 parts of acrylic acid, 2-4 parts of hydroxyethyl methacrylate, 5-6 parts of methyl methacrylate and 3-5 parts of mercapto POSS monomer.
2. The method for preparing the high weather-resistant self-cleaning reflective film according to claim 1, which is characterized in that: in the step (3), the ultraviolet curing time is 5-10 s, and the illumination intensity of ultraviolet light is 350-400 mW/cm 2 。
3. The method for preparing the high weather-resistant self-cleaning reflective film according to claim 1, which is characterized in that: when the pressure-sensitive adhesive is prepared, the dosage of the trimethylolpropane triacrylate is 0.8-1.5 wt% of the acrylate prepolymer, and the dosage of the TPO is 1.6-2.2 wt% of the acrylate prepolymer.
4. A reflective film produced by the method for producing a highly weather-resistant self-cleaning reflective film according to any one of claims 1 to 3.
CN202310124147.0A 2023-02-16 2023-02-16 High-weather-resistance self-cleaning reflective film and preparation method thereof Active CN116285730B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104263238A (en) * 2014-09-11 2015-01-07 天津大学 Fluoridated POSS (polysilsesquioxane) composite organic silicon coating as well as preparation method and anti-icing application thereof
WO2022062303A1 (en) * 2020-09-24 2022-03-31 中天科技精密材料有限公司 Gap reflective film and preparation method therefor, and photovoltaic module
CN114479665A (en) * 2022-02-25 2022-05-13 四川大学 High-transparency flexible scratch-resistant coating, functional coating and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104263238A (en) * 2014-09-11 2015-01-07 天津大学 Fluoridated POSS (polysilsesquioxane) composite organic silicon coating as well as preparation method and anti-icing application thereof
WO2022062303A1 (en) * 2020-09-24 2022-03-31 中天科技精密材料有限公司 Gap reflective film and preparation method therefor, and photovoltaic module
CN114479665A (en) * 2022-02-25 2022-05-13 四川大学 High-transparency flexible scratch-resistant coating, functional coating and preparation method thereof

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