WO2015180627A1 - Electromagnetic radiation-resistant protective film and preparation method thereof - Google Patents

Electromagnetic radiation-resistant protective film and preparation method thereof Download PDF

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Publication number
WO2015180627A1
WO2015180627A1 PCT/CN2015/079843 CN2015079843W WO2015180627A1 WO 2015180627 A1 WO2015180627 A1 WO 2015180627A1 CN 2015079843 W CN2015079843 W CN 2015079843W WO 2015180627 A1 WO2015180627 A1 WO 2015180627A1
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Prior art keywords
electromagnetic radiation
protection film
radiation protection
photocurable coating
silver powder
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PCT/CN2015/079843
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French (fr)
Chinese (zh)
Inventor
陈克勇
朱文峰
杨忠芝
吴建海
虞礼森
齐东东
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东莞市纳利光学材料有限公司
深圳比科斯电子股份有限公司
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Publication of WO2015180627A1 publication Critical patent/WO2015180627A1/en

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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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

Definitions

  • the invention relates to the technical field of optical protective films, in particular to an anti-electromagnetic radiation protection film and a preparation method thereof.
  • the invention patent of Japanese Patent Application No. 201310167462.8 discloses a low-emission coating composition comprising 1-15% of semiconductor nanoparticles, 1-10% of water-soluble conductive polymer material and 10-60% of silicone resin.
  • the low-emission coating composition can block ultraviolet rays to a certain extent, its main function is thermal insulation, and the amount of the silicone resin in the composition is large, and the anti-electromagnetic radiation effect is not satisfactory.
  • the object of the present invention is to provide an anti-electromagnetic radiation protection film and a preparation method thereof according to the deficiencies of the prior art, and the obtained optical protection film has good anti-electromagnetic wave effect, and the preparation process is simple and mature, and is favorable for popularization and application.
  • the present invention has been achieved by the following technical solutions.
  • a method for preparing an anti-electromagnetic radiation protection film comprising the following processing steps:
  • Step 1 Preparation of photocurable coating with anti-electromagnetic radiation function
  • Multi-wall/single-walled carbon nanotubes are heated and refluxed in boiling state with 40-80 times of concentrated concentrated nitric acid.
  • the carbon nanotubes are purified and surface-activated for 2-5 hours, then filtered and deionized. Washed with water to obtain treated carbon nanotubes; after carbon nanotube treatment, amorphous carbon, Fe, etc.
  • the mass is removed and the purity of the carbon nanotubes is over 95%.
  • the content of organic functional groups such as surface hydroxyl groups and carboxyl groups reaches about 10 mmol/g, and the degree of surface activation is high, which is easy to recombine.
  • the mass of concentrated nitric acid is 50 times the mass of the multi-wall/single-walled carbon nanotubes.
  • the concentrated nitric acid has a mass fraction of 70%, a density of about 1.4 g/cm3, and a boiling point of 83 °C.
  • the treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer.
  • the mass ratio of carbon nanotubes to aniline is 1:50-1:100, and then (NH 4 ) 2 S 2 O 8 is added dropwise.
  • the oxidative polymerization is carried out, and the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1 to 1:1.2, and the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum; preferably,
  • the mass ratio of carbon nanotubes to aniline is 1:60.
  • the carbon nanotube-polyaniline composite material is dispersed into an acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having an electromagnetic wave resistance effect, and the carbon nanotube-polyaniline composite material occupies the photocurable coating material.
  • the weight percentage is 3-8%; the carbon nanotube-polyaniline composite material acts as an additive material to resist electromagnetic radiation, and the acrylic urethane resin is hardened by UV curing.
  • Step 2 Apply the photocurable coating to the PET substrate with a micro-concave roll.
  • the coating thickness of the photocurable coating is 3-10 ⁇ m, the diameter of the micro-concave roll is 30-50 mm, and the number of micro-concave rolls is 40-400.
  • the coating thickness of the photocurable coating is 5-8 ⁇ m, the diameter of the micro concave roll is 40 mm, and the number of lines of the micro concave roll is 80-300.
  • Step 3 The coating is cured to form a film
  • the PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 8-13 m/min, and the light intensity of the UV lamp is 200-800 mj/cm 2 ; preferably, the conveying speed of the guiding roller
  • the light intensity of the UV lamp was 500 mj/cm 2 at 10 m/min.
  • the back surface of the PET substrate processed in the third step is coated with a liquid addition reaction silica gel, a liquid acrylic glue or a polyurethane glue having a thickness of 10-30 ⁇ m, baked in an oven, baked at a temperature of 130-200 ° C, and then affixed with PET.
  • the film is protected against electromagnetic radiation.
  • the glue has a thickness of 20 ⁇ m and a baking temperature of 150-180 °C.
  • the liquid addition reaction silica gel is polydimethylsiloxane, which has heat resistance, cold resistance, small viscosity change with temperature, water repellency, small surface tension, thermal conductivity, and thermal conductivity of 0.134-0.159 W/M*K.
  • Liquid acrylic glue is referred to as PMMA glue, also known as acrylic or plexiglass. Its cast-plate polymer has a number average molecular weight of 2.2 ⁇ 104 and a relative density of 1.19-1.20. 1.482-1.521, the moisture absorption is below 0.5%, and the glass transition temperature is 105 °C. With high transparency and low price.
  • Polyurethane glue is a glue containing a urethane group and an isocyanate group in the molecular chain. It has high reactivity with isocyanate and urethane groups. It has high reactivity and can be cured at room temperature. Therefore, it is suitable for metal, rubber, glass and ceramics. Plastic, wood, fabric, leather and other materials have excellent adhesive properties. The main chain of polyurethane is very flexible, and its biggest feature is to withstand shock and bending fatigue, high peel strength, especially excellent low temperature resistance.
  • the heating temperature is 150-180 ° C;
  • B acidic conditions, specifically adjusting the pH to 1-2 with HCl ;
  • C high-speed mixing equipment stirring speed of 800-1300 rev / min, ultrasonic dispersion equipment dispersion time is 3-5h.
  • the mass ratio of B, carbon nanotubes and aniline is 1:60-1:80, dried under vacuum for 20-40 min, drying temperature is 100 ° C, and vacuum degree is -75 kPa to -100 kPa.
  • the acrylic urethane resin is a 6-9 functional acrylic urethane resin.
  • the polyfunctional acrylic urethane resin is a non-functional acrylic urethane resin prepared by mixing biuret and pentaerythritol triacrylate in a molar ratio of 1:2-1:5.
  • the reaction temperature is 35-45 ° C, then the temperature is raised to 70-100 ° C, the temperature is maintained for 2-5 h, the reaction is carried out until the mass fraction of -NCO is 0-0.5%, and the mixture is cooled to room temperature to obtain a non-functional acrylic urethane.
  • the photocurable coating further comprises 1-5% by weight of gradation nano silver powder, and the gradation of the nano silver powder comprises 200 nm silver powder and 30 nm silver powder, 200 nm silver powder and 30 nm silver powder mass ratio. It is 1:7.
  • the nano-silver particles with small particle size during mixing can be embedded in the nano-silver particles with large particle size and between two adjacent nano-silver particles with a particle size of 200 nm.
  • the ratio of the silver powder to the mass of the silver powder having a particle diameter of 30 nm is 7:1, ensuring that the nano-silver powder of the large-sized nano-silver powder is uniformly coated with the small-sized nano-silver powder around the nano-silver powder, thereby making the nano-silver conductive particles more connected.
  • Tight, graded nano-silver powder forms a conductive mesh, which improves conductivity and has good anti-electromagnetic radiation effect.
  • the carbon nanotube-polyaniline composite material and the graded nano silver powder are dispersed into the acrylic polyurethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having an electromagnetic wave resistance effect.
  • the carbon nanotube-polyaniline composite material accounts for 3-8% by weight of the photocurable coating
  • the graded nano silver powder accounts for 1-5% by weight of the photocurable coating
  • the acrylic polyurethane resin accounts for the weight percentage of the photocurable coating. 87-96%.
  • the grading nano silver powder and the carbon nanotube-polyaniline composite material are dispersed together to the acrylic urethane resin to further enhance the anti-electromagnetic radiation effect of the carbon nanotube-polyaniline composite material, and the obtained protective film has good anti-electromagnetic radiation.
  • the PET substrate has a thickness of 25-200 ⁇ m, the PET substrate has a light transmittance of not less than 95%, the PET film has a thickness of 25-75 ⁇ m, and the PET film has a light transmittance of 92-95%.
  • the PET substrate has a thickness of 75-150 ⁇ m, the PET substrate has a light transmittance of 95-96%, the PET film has a thickness of 25-50 ⁇ m, and the PET film has a light transmittance of 92-93%.
  • the photocurable coating has a solid content of 40-50% and a viscosity of 50-100 cps.
  • the anti-electromagnetic radiation protection film prepared by the preparation method of the anti-electromagnetic radiation protection film has an optical transmittance of 90-93%.
  • the anti-electromagnetic radiation protection film of the invention has good anti-electromagnetic wave radiation effect, and the process is simple and mature, and is favorable for popularization and application.
  • the PET film can be peeled off to attach the anti-electromagnetic radiation protection film to the mobile phone or display screen.
  • the PET film can be peeled off to attach the anti-electromagnetic radiation protection film to the mobile phone or display screen.
  • it is simple to use. Convenient and easy to promote.
  • Carbon nanotube-polyaniline composite material the interface component has a large proportion, the unsaturated bond has many dangling bonds, and has high electromagnetic wave absorption performance. Compared with a single material, carbon nanotube-polyaniline composites have the advantages of absorption frequency bandwidth, low density, thin thickness and good compatibility.
  • the photocurable coating prepared by using carbon nanotube-polyaniline composite material significantly improves the compatibility of the system, so that the optical film absorbs electromagnetic waves, and the hardness and wear resistance of the photocurable coating layer can also remain normal. Level.
  • a method for preparing an anti-electromagnetic radiation protection film comprising the following processing steps:
  • Step 1 Preparation of photocurable coating with anti-electromagnetic radiation function
  • Multi-wall/single-walled carbon nanotubes are heated and refluxed under boiling conditions with 40 times of concentrated concentrated nitric acid. The heating temperature is 150 ° C.
  • the carbon nanotubes are purified and surface activated for 5 hours, then filtered and used. Washing with deionized water to obtain treated carbon nanotubes;
  • the treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer.
  • the acidic condition is to adjust the pH to 1 with HCl, the mass ratio of carbon nanotubes to aniline is 1:50, and then dropwise (NH 4 ) 2 S 2 O 8 is subjected to oxidative polymerization, and the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1, and the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum for 20 minutes. Drying temperature is 100 ° C, vacuum degree is -100 kPa;
  • the carbon nanotube-polyaniline composite material is dispersed into the acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, the stirring speed is 800 rpm, the dispersion time is 5 h, centrifugal filtration, and the photocurable coating with anti-electromagnetic effect is obtained.
  • the carbon nanotube-polyaniline composite material accounts for 3% by weight of the photocurable coating;
  • the acrylic urethane resin is a 6-functional acrylic polyurethane resin;
  • Step 2 coating the photocurable coating on the PET substrate with a micro concave roll, the coating thickness of the photocurable coating is 3 ⁇ m, the diameter of the micro concave roller is 30 mm, and the number of lines of the micro concave roller is 40; the PET substrate The thickness of the film is 25 ⁇ m, and the transmittance of the PET substrate is 95%;
  • Step 3 The coating is cured to form a film
  • the PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 8 m/min, and the light intensity of the UV lamp is 800 mj/cm 2 ;
  • a liquid addition reaction silica gel having a thickness of 10 ⁇ m is applied, baked in an oven, baked at a temperature of 130 ° C, and then a PET film is attached, and the thickness of the PET film is At 25 ⁇ m, the transmittance of the PET film was 92%, and an anti-electromagnetic radiation protection film was obtained.
  • the photocurable coating of the present embodiment has a solid content of 40% and a viscosity of 50 cps, and the obtained anti-electromagnetic radiation
  • the protective film has a light transmittance of 90%.
  • the photocurable coating further comprises a graded nano silver powder having a weight percentage of 1%, and the graded nano silver powder comprises 200 nm silver powder and The mass ratio of 30 nm silver powder, 200 nm silver powder and 30 nm silver powder is 1:7.
  • the carbon nanotube-polyaniline composite material and the graded nano silver powder were dispersed into acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having anti-electromagnetic wave effect, and the carbon nanotube-polyaniline composite material accounted for
  • the weight percentage of the photocurable coating is 3%
  • the weight percentage of the graded nano silver powder to the photocurable coating is 1%
  • the weight ratio of the acrylic polyurethane resin to the photocurable coating is 96%.
  • a method for preparing an anti-electromagnetic radiation protection film comprising the following processing steps:
  • Step 1 Preparation of photocurable coating with anti-electromagnetic radiation function
  • Multi-wall/single-walled carbon nanotubes are heated and refluxed under boiling conditions with 50 times of concentrated concentrated nitric acid. The heating temperature is 160 ° C.
  • the carbon nanotubes are purified and surface activated for 4.5 h, then filtered. And washing with deionized water to obtain treated carbon nanotubes;
  • the treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer.
  • the acidic condition is to adjust the pH to 1 with HCl, the mass ratio of carbon nanotubes to aniline is 1:60, and then dropwise (NH 4 ) 2 S 2 O 8 is subjected to oxidative polymerization, and the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1, and the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum for 20 minutes. Drying temperature is 100 ° C, vacuum degree is -90 kPa;
  • the carbon nanotube-polyaniline composite material is dispersed into the acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, the stirring speed is 900 rpm, the dispersion time is 4.5 h, centrifugal filtration, and the light curing with electromagnetic wave resistance is obtained.
  • the coating, the carbon nanotube-polyaniline composite material accounts for 4% by weight of the photocurable coating;
  • the acrylic urethane resin is a 7-functional acrylic polyurethane resin;
  • Step 2 coating the photocurable coating on the PET substrate with a micro concave roll, the coating thickness of the photocurable coating is 5 ⁇ m, the diameter of the micro concave roller is 35 mm, and the number of lines of the micro concave roller is 80; the PET substrate The thickness of the film is 75 ⁇ m, and the transmittance of the PET substrate is 95%;
  • Step 3 The coating is cured to form a film
  • the PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 9 m/min, and the light intensity of the UV lamp is 600 mj/cm 2 ;
  • a liquid addition reaction silica gel having a thickness of 15 ⁇ m is applied, baked in an oven, baked at a temperature of 150 ° C, and then a PET film is attached, and the thickness of the PET film is At 30 ⁇ m, the transmittance of the PET film was 92%, and an anti-electromagnetic radiation protection film was obtained.
  • the photocurable coating of the present embodiment has a solid content of 42% and a viscosity of 60 cps, and the prepared electromagnetic radiation protection film has a light transmittance of 90%.
  • the photocurable coating further comprises a graded nano silver powder having a weight percentage of 2%, and the graded nano silver powder comprises 200 nm silver powder and The mass ratio of 30 nm silver powder, 200 nm silver powder and 30 nm silver powder is 1:7.
  • the carbon nanotube-polyaniline composite material and the graded nano silver powder were dispersed into acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having anti-electromagnetic wave effect, and the carbon nanotube-polyaniline composite material accounted for
  • the weight percentage of the photocurable coating was 4%
  • the weight percentage of the graded nanosilver powder to the photocurable coating was 2%
  • the weight ratio of the acrylic polyurethane resin to the photocurable coating was 94%.
  • a method for preparing an anti-electromagnetic radiation protection film comprising the following processing steps:
  • Step 1 Preparation of photocurable coating with anti-electromagnetic radiation function
  • Multi-wall/single-walled carbon nanotubes are heated and refluxed in boiling state with 60 times of concentrated concentrated nitric acid.
  • the heating temperature is 170 ° C, and the carbon nanotubes are purified and surface activated for 4 hours, then filtered and used. Washing with deionized water to obtain treated carbon nanotubes;
  • the treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer.
  • the acidic condition is to adjust the pH to 1.5 with HCl, the mass ratio of carbon nanotubes to aniline is 1:70, and then dropwise (NH 4 ) 2 S 2 O 8 is subjected to oxidative polymerization, and the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1, and the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum for 30 minutes. Drying temperature is 100 ° C, vacuum degree is -85 kPa;
  • the carbon nanotube-polyaniline composite material is dispersed into the acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, the stirring speed is 1000 rpm, the dispersion time is 4 h, centrifugal filtration, and the photocurable coating with anti-electromagnetic effect is obtained.
  • the carbon nanotube-polyaniline composite material accounts for 5% by weight of the photocurable coating;
  • the acrylic urethane resin is an 8-functional acrylic polyurethane resin;
  • Step 2 coating the photocurable coating on the PET substrate with a micro concave roll, the coating thickness of the photocurable coating is 6 ⁇ m, the diameter of the micro concave roller is 40 mm, and the number of lines of the micro concave roller is 150; the PET substrate The thickness of the film is 100 ⁇ m, and the transmittance of the PET substrate is 96%;
  • Step 3 The coating is cured to form a film
  • the PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 10 m/min, and the light intensity of the UV lamp is 500 mj/cm 2 ;
  • the back surface of the processed PET substrate is coated with a liquid acrylic glue having a thickness of 20 ⁇ m, baked in an oven, baked at a temperature of 160 ° C, and then attached with a PET film having a thickness of 50 ⁇ m.
  • the transmittance of the PET film is 93%, and an anti-electromagnetic radiation protection film is obtained.
  • the photocurable coating of the present embodiment has a solid content of 45% and a viscosity of 70 cps, and the prepared electromagnetic radiation protection film has a light transmittance of 91%.
  • the photocurable coating further comprises a grading nano silver powder in a weight percentage of 3%, and the grading nano silver powder comprises 200 nm silver powder and The mass ratio of 30 nm silver powder, 200 nm silver powder and 30 nm silver powder is 1:7.
  • the carbon nanotube-polyaniline composite material and the graded nano silver powder were dispersed into acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having anti-electromagnetic wave effect, and the carbon nanotube-polyaniline composite material accounted for
  • the weight percentage of the photocurable coating was 5%
  • the weight percentage of the graded nanosilver powder to the photocurable coating was 3%
  • the weight ratio of the acrylic polyurethane resin to the photocurable coating was 92%.
  • a method for preparing an anti-electromagnetic radiation protection film comprising the following processing steps:
  • Step 1 Preparation of photocurable coating with anti-electromagnetic radiation function
  • Multi-wall/single-walled carbon nanotubes are heated and refluxed in boiling state with 70 times of concentrated concentrated nitric acid. The heating temperature is 180 ° C.
  • the carbon nanotubes are purified and surface activated for 3 hours, then filtered and used. Washing with deionized water to obtain treated carbon nanotubes;
  • the treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer.
  • the acidic condition is to adjust the pH to 2 with HCl, the mass ratio of carbon nanotubes to aniline is 1:80, and then dropwise (NH 4 ) 2 S 2 O 8 is oxidatively polymerized, the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1.1, the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum for 30 min. Drying temperature is 100 ° C, vacuum degree is -80 kPa;
  • the carbon nanotube-polyaniline composite material is dispersed into the acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, the stirring speed is 1100 rpm, the dispersion time is 3.5 h, centrifugal filtration, and the light curing with electromagnetic wave resistance is obtained.
  • the coating, the carbon nanotube-polyaniline composite material accounts for 6% by weight of the photocurable coating;
  • the acrylic urethane resin is a 9-functional acrylic polyurethane resin;
  • Step 2 coating the photocurable coating on the PET substrate with a micro concave roll, the coating thickness of the photocurable coating is 8 ⁇ m, the diameter of the micro concave roller is 45 mm, and the number of lines of the micro concave roller is 200; the PET substrate The thickness of the film is 150 ⁇ m, and the transmittance of the PET substrate is 96%;
  • Step 3 The coating is cured to form a film
  • the PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 12 m/min, and the light intensity of the UV lamp is 350 mj/cm 2 ;
  • a liquid acrylic glue having a thickness of 25 ⁇ m is applied, baked in an oven, baked at a temperature of 180 ° C, and then a PET film is attached, and the thickness of the PET film is 60 ⁇ m.
  • the transmittance of the PET film is 94%, and an anti-electromagnetic radiation protection film is obtained.
  • the photocurable coating of the present embodiment has a solid content of 48% and a viscosity of 80 cps, and the prepared electromagnetic radiation protection film has a light transmittance of 92%.
  • the photocurable coating further comprises a graded nano silver powder having a weight percentage of 4%, and the graded nano silver powder comprises 200 nm silver powder and The mass ratio of 30 nm silver powder, 200 nm silver powder and 30 nm silver powder is 1:7.
  • the carbon nanotube-polyaniline composite material and the graded nano silver powder were dispersed into acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having anti-electromagnetic wave effect, and the carbon nanotube-polyaniline composite material accounted for
  • the weight percentage of the photocurable coating is 6%
  • the weight percentage of the graded nano silver powder to the photocurable coating is 4%
  • the weight ratio of the acrylic polyurethane resin to the photocurable coating is 90%.
  • a method for preparing an anti-electromagnetic radiation protection film comprising the following processing steps:
  • Step 1 Preparation of photocurable coating with anti-electromagnetic radiation function
  • Multi-wall/single-walled carbon nanotubes are heated and refluxed in boiling state with 80 times of concentrated concentrated nitric acid. The heating temperature is 150 ° C.
  • the carbon nanotubes are purified and surface activated for 2 hours, then filtered and used. Washing with deionized water to obtain treated carbon nanotubes;
  • the treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer.
  • the acidic condition is to adjust the pH to 2 with HCl, the mass ratio of carbon nanotubes to aniline is 1:100, and then dropwise (NH 4 ) 2 S 2 O 8 is subjected to oxidative polymerization, and the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1.2, and the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum for 40 min. Drying temperature is 100 ° C, vacuum degree is -75 kPa;
  • the carbon nanotube-polyaniline composite material is dispersed into the acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, the stirring speed is 1300 rpm, the dispersion time is 3 h, centrifugal filtration, and the photocurable coating with anti-electromagnetic effect is obtained.
  • the carbon nanotube-polyaniline composite material accounts for 8% by weight of the photocurable coating;
  • the acrylic urethane resin is a 9-functional acrylic polyurethane resin;
  • Step 2 coating the photocurable coating on the PET substrate with a micro concave roll, the coating thickness of the photocurable coating is 10 ⁇ m, the diameter of the micro concave roller is 50 mm, and the number of lines of the micro concave roller is 400; the PET substrate The thickness of the film is 200 ⁇ m, and the transmittance of the PET substrate is 95%;
  • Step 3 The coating is cured to form a film
  • the PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 13 m/min, and the light intensity of the UV lamp is 200 mj/cm 2 ;
  • a polyurethane glue having a thickness of 30 ⁇ m is applied on the back side of the PET substrate processed in the third step.
  • the oven was baked at a baking temperature of 200 ° C, and then a PET film was attached.
  • the thickness of the PET film was 75 ⁇ m, and the transmittance of the PET film was 95% to obtain an anti-electromagnetic radiation protection film.
  • the photocurable coating of the present embodiment has a solid content of 50% and a viscosity of 100 cps, and the prepared electromagnetic radiation protection film has a light transmittance of 93%.
  • the present embodiment is different from the embodiment 9 in that, in the embodiment, the step 1, C, the photocurable coating further comprises a 5% by weight of gradation nano silver powder, and the grading nano silver powder comprises 200 nm silver powder and The mass ratio of 30 nm silver powder, 200 nm silver powder and 30 nm silver powder is 1:7.
  • the carbon nanotube-polyaniline composite material and the graded nano silver powder were dispersed into acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having anti-electromagnetic wave effect, and the carbon nanotube-polyaniline composite material accounted for
  • the weight percentage of the photocurable coating is 8%, the weight percentage of the graded nano silver powder to the photocurable coating is 5%, and the weight ratio of the acrylic polyurethane resin to the photocurable coating is 87%.

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Abstract

The present invention relates to the technical field of optical protective films, particularly to an electromagnetic radiation-resistant protective film and preparation method thereof, the preparation method comprising the following steps: step one, preparing a photocureable coating having an electromagnetic radiation-resistant function; step two, applying the photocureable coating to a PET substrate via a slightly concave roller, the coating thickness of the photocureable coating being 3 μm-10 μm, the diameter of the slightly concave roller being 30 mm-50 mm, and the number of lines of the slightly concave roller being 40-400; step three, solidifying the coating to form a film; and step four, preparing the electromagnetic radiation resistant protective film. The electromagnetic radiation-resistant protective film of the present invention has good electromagnetic wave radiation-resistant effect, and a simple and mature process, and is easy to promote and apply. When being used, the electromagnetic -radiation-resistant PET protective film can be attached to a mobile phone or a display screen after being torn off, and is easier and more convenient to promote compared with other electromagnetic radiation-resistant devices at home and abroad such as radiation-protective clothes and electromagnetic wave protective helmets.

Description

一种抗电磁辐射保护膜及其制备方法Anti-electromagnetic radiation protection film and preparation method thereof 技术领域Technical field
本发明涉及光学保护膜技术领域，尤其涉及一种抗电磁辐射保护膜及其制备方法。The invention relates to the technical field of optical protective films, in particular to an anti-electromagnetic radiation protection film and a preparation method thereof.
背景技术Background technique
目前，移动通信已经成为现代社会的标志之一，它不仅使人们随时随地都可以保持和外界的沟通联系，而且还可以通过手机接入互联网，为人们的日常生活和工作带来了极大的便利。但与此同时，移动通信的电磁辐射也成为危害人们健康的污染之一。为了防止移动设备的正面辐射，很多保护膜厂商开始研发具有抗电磁波辐射的保护膜。At present, mobile communication has become one of the symbols of modern society. It not only enables people to maintain communication with the outside world anytime and anywhere, but also can access the Internet through mobile phones, bringing great benefits to people's daily life and work. convenient. At the same time, however, the electromagnetic radiation of mobile communications has become one of the pollutions that endanger people's health. In order to prevent frontal radiation of mobile devices, many protective film manufacturers have begun to develop protective films with anti-electromagnetic radiation.
中国专利申请号为201310167462.8的发明专利公开了一种低辐射涂料组合物，包括1-15％的半导体纳米颗粒，1-10％的水溶性导电高分子材料和10-60％的有机硅树脂。该低辐射涂料组合物虽在一定程度上能阻隔紫外线，但其主要作用是保温隔热，且该组合物中有机硅树脂的用量较大，抗电磁波辐射效果不理想。The invention patent of Japanese Patent Application No. 201310167462.8 discloses a low-emission coating composition comprising 1-15% of semiconductor nanoparticles, 1-10% of water-soluble conductive polymer material and 10-60% of silicone resin. Although the low-emission coating composition can block ultraviolet rays to a certain extent, its main function is thermal insulation, and the amount of the silicone resin in the composition is large, and the anti-electromagnetic radiation effect is not satisfactory.
发明内容Summary of the invention
本发明的目的在于针对现有技术的不足，提供一种抗电磁辐射保护膜及其制备方法，制得的光学保护膜抗电磁波效果好，制备工艺简单、成熟，有利于推广应用。The object of the present invention is to provide an anti-electromagnetic radiation protection film and a preparation method thereof according to the deficiencies of the prior art, and the obtained optical protection film has good anti-electromagnetic wave effect, and the preparation process is simple and mature, and is favorable for popularization and application.
本发明是通过以下技术方案来实现的。The present invention has been achieved by the following technical solutions.
一种抗电磁辐射保护膜的制备方法，包括以下加工步骤：A method for preparing an anti-electromagnetic radiation protection film, comprising the following processing steps:
步骤一：具有抗电磁辐射功能的光固化涂料的制备Step 1: Preparation of photocurable coating with anti-electromagnetic radiation function
A、采用多壁/单壁碳纳米管利用40-80倍质量的浓硝酸在沸腾状态下加热回流处理，对碳纳米管进行纯化与表面活化，反应时间为2-5h，然后过滤并用去离子水洗涤，得到处理后的碳纳米管；碳纳米管处理后，无定形碳、Fe等杂 质被除去，碳纳米管纯度达到95％以上。表面羟基、羧基等有机官能团含量达到10mmol/g左右，表面活化程度高，易于复合。优选地，浓硝酸的质量为多壁/单壁碳纳米管的质量的50倍。浓硝酸的质量分数为70％，密度约为1.4g/cm3，沸点为83℃。A. Multi-wall/single-walled carbon nanotubes are heated and refluxed in boiling state with 40-80 times of concentrated concentrated nitric acid. The carbon nanotubes are purified and surface-activated for 2-5 hours, then filtered and deionized. Washed with water to obtain treated carbon nanotubes; after carbon nanotube treatment, amorphous carbon, Fe, etc. The mass is removed and the purity of the carbon nanotubes is over 95%. The content of organic functional groups such as surface hydroxyl groups and carboxyl groups reaches about 10 mmol/g, and the degree of surface activation is high, which is easy to recombine. Preferably, the mass of concentrated nitric acid is 50 times the mass of the multi-wall/single-walled carbon nanotubes. The concentrated nitric acid has a mass fraction of 70%, a density of about 1.4 g/cm3, and a boiling point of 83 °C.
B、将处理后的碳纳米管与苯胺在酸性条件下混合形成预聚体，碳纳米管与苯胺的质量比为1:50-1:100，然后滴加(NH4)2S2O8进行氧化聚合，(NH4)2S2O8与苯胺的摩尔比为1:1-1:1.2，得到碳纳米管-聚苯胺复合材料，过滤，洗涤，在真空条件下干燥；优选地，碳纳米管与苯胺的质量比为1:60。B. The treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer. The mass ratio of carbon nanotubes to aniline is 1:50-1:100, and then (NH 4 ) 2 S 2 O 8 is added dropwise. The oxidative polymerization is carried out, and the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1 to 1:1.2, and the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum; preferably, The mass ratio of carbon nanotubes to aniline is 1:60.
C、将碳纳米管-聚苯胺复合材料通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为3-8％；碳纳米管-聚苯胺复合材料作为添加材料起到抗电磁辐射作用，丙烯酸聚氨酯树脂经UV固化后，起到硬化作用。C. The carbon nanotube-polyaniline composite material is dispersed into an acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having an electromagnetic wave resistance effect, and the carbon nanotube-polyaniline composite material occupies the photocurable coating material. The weight percentage is 3-8%; the carbon nanotube-polyaniline composite material acts as an additive material to resist electromagnetic radiation, and the acrylic urethane resin is hardened by UV curing.
步骤二：将光固化涂料用微凹辊涂布在PET基材上，光固化涂料的涂布厚度3-10μm，微凹辊的直径为30-50mm，微凹辊的线数为40-400；优选地，光固化涂料的涂布厚度5-8μm，微凹辊的直径为40mm，微凹辊的线数为80-300。Step 2: Apply the photocurable coating to the PET substrate with a micro-concave roll. The coating thickness of the photocurable coating is 3-10 μm, the diameter of the micro-concave roll is 30-50 mm, and the number of micro-concave rolls is 40-400. Preferably, the coating thickness of the photocurable coating is 5-8 μm, the diameter of the micro concave roll is 40 mm, and the number of lines of the micro concave roll is 80-300.
步骤三：涂料固化成膜Step 3: The coating is cured to form a film
将步骤二加工后的PET基材经导辊送达UV灯箱，导辊的输送速度为8-13m/min，UV灯的光强为200-800mj/cm2；优选地，导辊的输送速度为10m/min，UV灯的光强为500mj/cm2。The PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 8-13 m/min, and the light intensity of the UV lamp is 200-800 mj/cm 2 ; preferably, the conveying speed of the guiding roller The light intensity of the UV lamp was 500 mj/cm 2 at 10 m/min.
步骤四：制备抗电磁辐射保护膜Step 4: Preparation of anti-electromagnetic radiation protection film
在步骤三加工后的PET基材的背面涂覆厚度为10-30μm的液态加成型反应硅胶、液态亚克力胶水或聚氨酯胶水，经过烘箱烘烤，烘烤温度为130-200℃，然后贴上PET护膜，制得抗电磁辐射保护膜。优选地，胶水的厚度为20μm，烘烤温度为150-180℃。The back surface of the PET substrate processed in the third step is coated with a liquid addition reaction silica gel, a liquid acrylic glue or a polyurethane glue having a thickness of 10-30 μm, baked in an oven, baked at a temperature of 130-200 ° C, and then affixed with PET. The film is protected against electromagnetic radiation. Preferably, the glue has a thickness of 20 μm and a baking temperature of 150-180 °C.
液态加成型反应硅胶为聚二甲基硅氧烷，耐热性、耐寒性、黏度随温度变化小、防水性、表面张力小、具有导热性，导热系数为0.134-0.159W/M*K。The liquid addition reaction silica gel is polydimethylsiloxane, which has heat resistance, cold resistance, small viscosity change with temperature, water repellency, small surface tension, thermal conductivity, and thermal conductivity of 0.134-0.159 W/M*K.
液态亚克力胶水简称PMMA胶水，又称为压克力或有机玻璃，它的铸板聚合物的数均分子量一般为2.2×104，相对密度为1.19-1.20，折射率为 1.482-1.521，吸湿度在0.5％以下，玻璃化温度为105℃。具有高透明度，低价格。Liquid acrylic glue is referred to as PMMA glue, also known as acrylic or plexiglass. Its cast-plate polymer has a number average molecular weight of 2.2×104 and a relative density of 1.19-1.20. 1.482-1.521, the moisture absorption is below 0.5%, and the glass transition temperature is 105 °C. With high transparency and low price.
聚氨酯胶水是分子链中含有氨酯基和异氰酸酯基的胶水，由于含有强极性的异氰酸酯和氨基甲酸酯基，具有很高的反应性，能够室温固化，因而对金属、橡胶、玻璃、陶瓷、塑料、木材、织物、皮革等多种材料都有优良的胶粘性能。聚氨酯的主链柔性很好，其最大特点是耐受冲击震动和弯曲疲劳，剥离强度很高，特别是耐低温性能极其优异。Polyurethane glue is a glue containing a urethane group and an isocyanate group in the molecular chain. It has high reactivity with isocyanate and urethane groups. It has high reactivity and can be cured at room temperature. Therefore, it is suitable for metal, rubber, glass and ceramics. Plastic, wood, fabric, leather and other materials have excellent adhesive properties. The main chain of polyurethane is very flexible, and its biggest feature is to withstand shock and bending fatigue, high peel strength, especially excellent low temperature resistance.
其中，所述步骤一中，A、多壁/单壁碳纳米管和浓硝酸的加热回流处理中，加热温度为150-180℃；B、酸性条件，具体为用HCl调节pH为1-2；C、高速搅拌设备的搅拌速度为800-1300转/min，超声波分散设备的分散时间是3-5h。Wherein, in the first step, in the heating and refluxing treatment of A, multi-wall/single-walled carbon nanotubes and concentrated nitric acid, the heating temperature is 150-180 ° C; B, acidic conditions, specifically adjusting the pH to 1-2 with HCl ; C, high-speed mixing equipment stirring speed of 800-1300 rev / min, ultrasonic dispersion equipment dispersion time is 3-5h.
其中，所述步骤一中，B、碳纳米管与苯胺的质量比为1:60-1:80，真空条件下干燥20-40min，干燥温度为100℃，真空度为-75kPa到-100kPa。Wherein, in the first step, the mass ratio of B, carbon nanotubes and aniline is 1:60-1:80, dried under vacuum for 20-40 min, drying temperature is 100 ° C, and vacuum degree is -75 kPa to -100 kPa.
其中，所述步骤一中，C、所述丙烯酸聚氨酯树脂为6-9官能度丙烯酸聚氨酯树脂。Wherein, in the first step, C, the acrylic urethane resin is a 6-9 functional acrylic urethane resin.
具体地，所述多官能度丙烯酸聚氨酯树脂为九官能度丙烯酸聚氨酯树脂，其制备方法为：将缩二脲和季戊四醇三丙烯酸酯以摩尔质量比为1:2-1:5的比例混合，维持反应温度在35-45℃，然后升温至70-100℃，保温2-5h，反应至-NCO的质量分数为0-0.5％，冷却至室温制得九官能度丙烯酸聚氨酯。Specifically, the polyfunctional acrylic urethane resin is a non-functional acrylic urethane resin prepared by mixing biuret and pentaerythritol triacrylate in a molar ratio of 1:2-1:5. The reaction temperature is 35-45 ° C, then the temperature is raised to 70-100 ° C, the temperature is maintained for 2-5 h, the reaction is carried out until the mass fraction of -NCO is 0-0.5%, and the mixture is cooled to room temperature to obtain a non-functional acrylic urethane.
九官能度聚氨酯丙烯酸酯具有较快的固化速度和较好的机械强度，有9个“C＝C”双键，反应活性高(在1kW高压汞灯条件下，4s实干)，同时能有效提高涂膜的交联密度，显著地提高表面硬度，其铅笔硬度达3H以上，能显著提高涂层的耐磨性，且UV固化效果好。Nine-functional urethane acrylate has fast curing speed and good mechanical strength. It has 9 “C=C” double bonds and high reactivity (4s solid drying under 1kW high pressure mercury lamp), and can effectively improve The cross-linking density of the coating film significantly increases the surface hardness, and the pencil hardness of 3H or more can significantly improve the wear resistance of the coating, and the UV curing effect is good.
其中，所述步骤一中，C、所述光固化涂料还包括有重量百分比为1-5％的级配纳米银粉，级配纳米银粉包括200nm银粉和30nm银粉，200nm银粉和30nm银粉的质量比为1:7。Wherein, in the first step, C, the photocurable coating further comprises 1-5% by weight of gradation nano silver powder, and the gradation of the nano silver powder comprises 200 nm silver powder and 30 nm silver powder, 200 nm silver powder and 30 nm silver powder mass ratio. It is 1:7.
由于加入粒径大小不同的纳米银颗粒，混合时粒径小的纳米银颗粒可嵌入粒径大的纳米银颗粒内部以及相邻两个粒径大的纳米银颗粒之间，粒径200纳米的银粉与所述粒径30纳米的银粉的质量之比为7:1，确保大粒径的纳米银粉的四周和内部均匀包覆有小粒径的纳米银粉，从而使纳米银导电颗粒连接更加 紧密，级配纳米银粉形成一导电网，提高导电率，抗电磁波辐射效果好。Due to the addition of nano-silver particles with different particle sizes, the nano-silver particles with small particle size during mixing can be embedded in the nano-silver particles with large particle size and between two adjacent nano-silver particles with a particle size of 200 nm. The ratio of the silver powder to the mass of the silver powder having a particle diameter of 30 nm is 7:1, ensuring that the nano-silver powder of the large-sized nano-silver powder is uniformly coated with the small-sized nano-silver powder around the nano-silver powder, thereby making the nano-silver conductive particles more connected. Tight, graded nano-silver powder forms a conductive mesh, which improves conductivity and has good anti-electromagnetic radiation effect.
其中，所述步骤一中，C、将碳纳米管-聚苯胺复合材料和级配纳米银粉通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为3-8％，级配纳米银粉占光固化涂料的重量百分比为1-5％，丙烯酸聚氨酯树脂占光固化涂料的重量百分比为87-96％。将级配纳米银粉与碳纳米管-聚苯胺复合材料一同分散到丙烯酸聚氨酯树脂，进一步增强碳纳米管-聚苯胺复合材料的抗电磁辐射效果，制得的保护膜的抗电磁波辐射性好。Wherein, in the first step, C, the carbon nanotube-polyaniline composite material and the graded nano silver powder are dispersed into the acrylic polyurethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having an electromagnetic wave resistance effect. The carbon nanotube-polyaniline composite material accounts for 3-8% by weight of the photocurable coating, the graded nano silver powder accounts for 1-5% by weight of the photocurable coating, and the acrylic polyurethane resin accounts for the weight percentage of the photocurable coating. 87-96%. The grading nano silver powder and the carbon nanotube-polyaniline composite material are dispersed together to the acrylic urethane resin to further enhance the anti-electromagnetic radiation effect of the carbon nanotube-polyaniline composite material, and the obtained protective film has good anti-electromagnetic radiation.
其中，所述PET基材的厚度为25-200μm，PET基材的透光率不小于95％，所述PET护膜的厚度为25-75μm，PET护膜的透光率为92-95％。优选地，PET基材的厚度为75-150μm，PET基材的透光率为95-96％，所述PET护膜的厚度为25-50μm，PET护膜的透光率为92-93％。Wherein, the PET substrate has a thickness of 25-200 μm, the PET substrate has a light transmittance of not less than 95%, the PET film has a thickness of 25-75 μm, and the PET film has a light transmittance of 92-95%. . Preferably, the PET substrate has a thickness of 75-150 μm, the PET substrate has a light transmittance of 95-96%, the PET film has a thickness of 25-50 μm, and the PET film has a light transmittance of 92-93%. .
步骤一中，制得的光固化涂料的固含量为40-50％，粘度为50-100cps。In the first step, the photocurable coating has a solid content of 40-50% and a viscosity of 50-100 cps.
一种抗电磁辐射保护膜的制备方法制得的抗电磁辐射保护膜，抗电磁辐射保护膜的透光率为90-93％。The anti-electromagnetic radiation protection film prepared by the preparation method of the anti-electromagnetic radiation protection film has an optical transmittance of 90-93%.
本发明的有益效果为：The beneficial effects of the invention are:
(1)本发明的抗电磁辐射保护膜的抗电磁波辐射效果好，工艺简单、成熟，有利于推广应用。使用时，将PET护膜撕开即可将抗电磁辐射保护膜贴附在手机或显示屏上，与其它国内外防电磁辐射的装备，比如防辐射服、电磁波防护头盔等相比，使用简单方便，易于推广。(1) The anti-electromagnetic radiation protection film of the invention has good anti-electromagnetic wave radiation effect, and the process is simple and mature, and is favorable for popularization and application. When used, the PET film can be peeled off to attach the anti-electromagnetic radiation protection film to the mobile phone or display screen. Compared with other anti-electromagnetic radiation equipment at home and abroad, such as radiation protection suits and electromagnetic wave protection helmets, it is simple to use. Convenient and easy to promote.
(2)碳纳米管-聚苯胺复合材料，界面组元所占比例大，不饱和键悬挂键多，具有很高的电磁波吸收性能。相对于单一材料，碳纳米管-聚苯胺复合材料具有吸波频带宽、密度低、厚度薄、兼容性好等优点。(2) Carbon nanotube-polyaniline composite material, the interface component has a large proportion, the unsaturated bond has many dangling bonds, and has high electromagnetic wave absorption performance. Compared with a single material, carbon nanotube-polyaniline composites have the advantages of absorption frequency bandwidth, low density, thin thickness and good compatibility.
(3)采用碳纳米管-聚苯胺复合材料制得的光固化涂料显著改善了体系的兼容性，使光学膜在具有吸收电磁波的同时，光固化涂料层的硬度和耐磨性能也可以保持正常水平。(3) The photocurable coating prepared by using carbon nanotube-polyaniline composite material significantly improves the compatibility of the system, so that the optical film absorbs electromagnetic waves, and the hardness and wear resistance of the photocurable coating layer can also remain normal. Level.
(4)将碳纳米管-聚苯胺复合材料与级配纳米银粉一同分散到丙烯酸聚氨酯树脂，充分发挥级配纳米银粉的导电性和抗电磁波辐射性能，进一步增强碳纳米管-聚苯胺复合材料的抗电磁辐射效果，制得的保护膜的抗电磁波辐射性能 优异。(4) Dispersing the carbon nanotube-polyaniline composite material together with the graded nano silver powder to the acrylic polyurethane resin, fully exerting the conductivity and anti-electromagnetic radiation properties of the graded nano silver powder, and further enhancing the carbon nanotube-polyaniline composite material. Anti-electromagnetic radiation effect, anti-electromagnetic radiation performance of the prepared protective film Excellent.
具体实施方式detailed description
下面结合实施例对本发明作进一步的说明。The present invention will be further described below in conjunction with the embodiments.
实施例1。Example 1.
一种抗电磁辐射保护膜的制备方法，包括以下加工步骤：A method for preparing an anti-electromagnetic radiation protection film, comprising the following processing steps:
步骤一：具有抗电磁辐射功能的光固化涂料的制备Step 1: Preparation of photocurable coating with anti-electromagnetic radiation function
A、采用多壁/单壁碳纳米管利用40倍质量的浓硝酸在沸腾状态下加热回流处理，加热温度为150℃，对碳纳米管进行纯化与表面活化，反应时间为5h，然后过滤并用去离子水洗涤，得到处理后的碳纳米管；A. Multi-wall/single-walled carbon nanotubes are heated and refluxed under boiling conditions with 40 times of concentrated concentrated nitric acid. The heating temperature is 150 ° C. The carbon nanotubes are purified and surface activated for 5 hours, then filtered and used. Washing with deionized water to obtain treated carbon nanotubes;
B、将处理后的碳纳米管与苯胺在酸性条件下混合形成预聚体，酸性条件为用HCl调节pH为1，碳纳米管与苯胺的质量比为1:50，然后滴加(NH4)2S2O8进行氧化聚合，(NH4)2S2O8与苯胺的摩尔比为1:1，得到碳纳米管-聚苯胺复合材料，过滤，洗涤，在真空条件下干燥20min，干燥温度为100℃，真空度为-100kPa；B. The treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer. The acidic condition is to adjust the pH to 1 with HCl, the mass ratio of carbon nanotubes to aniline is 1:50, and then dropwise (NH 4 ) 2 S 2 O 8 is subjected to oxidative polymerization, and the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1, and the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum for 20 minutes. Drying temperature is 100 ° C, vacuum degree is -100 kPa;
C、将碳纳米管-聚苯胺复合材料通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，搅拌速度为800转/min，分散时间是5h，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为3％；所述丙烯酸聚氨酯树脂为6官能度丙烯酸聚氨酯树脂；C. The carbon nanotube-polyaniline composite material is dispersed into the acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, the stirring speed is 800 rpm, the dispersion time is 5 h, centrifugal filtration, and the photocurable coating with anti-electromagnetic effect is obtained. , the carbon nanotube-polyaniline composite material accounts for 3% by weight of the photocurable coating; the acrylic urethane resin is a 6-functional acrylic polyurethane resin;
步骤二：将光固化涂料用微凹辊涂布在PET基材上，光固化涂料的涂布厚度3μm，微凹辊的直径为30mm，微凹辊的线数为40；所述PET基材的厚度为25μm，PET基材的透光率95％；Step 2: coating the photocurable coating on the PET substrate with a micro concave roll, the coating thickness of the photocurable coating is 3 μm, the diameter of the micro concave roller is 30 mm, and the number of lines of the micro concave roller is 40; the PET substrate The thickness of the film is 25 μm, and the transmittance of the PET substrate is 95%;
步骤三：涂料固化成膜Step 3: The coating is cured to form a film
将步骤二加工后的PET基材经导辊送达UV灯箱，导辊的输送速度为8m/min，UV灯的光强为800mj/cm2；The PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 8 m/min, and the light intensity of the UV lamp is 800 mj/cm 2 ;
步骤四：制备抗电磁辐射保护膜Step 4: Preparation of anti-electromagnetic radiation protection film
在步骤三加工后的PET基材的背面涂覆厚度为10μm的液态加成型反应硅胶，经过烘箱烘烤，烘烤温度为130℃，然后贴上PET护膜，所述PET护膜的厚度为25μm，PET护膜的透光率为92％，制得抗电磁辐射保护膜。On the back side of the PET substrate processed in the third step, a liquid addition reaction silica gel having a thickness of 10 μm is applied, baked in an oven, baked at a temperature of 130 ° C, and then a PET film is attached, and the thickness of the PET film is At 25 μm, the transmittance of the PET film was 92%, and an anti-electromagnetic radiation protection film was obtained.
本实施例的光固化涂料的固含量为40％，粘度为50cps，制得的抗电磁辐射 保护膜透光率为90％。The photocurable coating of the present embodiment has a solid content of 40% and a viscosity of 50 cps, and the obtained anti-electromagnetic radiation The protective film has a light transmittance of 90%.
实施例2。Example 2.
本实施例与实施例1的不同之处在于：本实施例中，步骤一，C、所述光固化涂料还包括有重量百分比为1％的级配纳米银粉，级配纳米银粉包括200nm银粉和30nm银粉，200nm银粉和30nm银粉的质量比为1:7。The difference between the embodiment and the embodiment 1 is that, in the embodiment, the step 1, C, the photocurable coating further comprises a graded nano silver powder having a weight percentage of 1%, and the graded nano silver powder comprises 200 nm silver powder and The mass ratio of 30 nm silver powder, 200 nm silver powder and 30 nm silver powder is 1:7.
将碳纳米管-聚苯胺复合材料和级配纳米银粉通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为3％，级配纳米银粉占光固化涂料的重量百分比为1％，丙烯酸聚氨酯树脂占光固化涂料的重量百分比为96％。The carbon nanotube-polyaniline composite material and the graded nano silver powder were dispersed into acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having anti-electromagnetic wave effect, and the carbon nanotube-polyaniline composite material accounted for The weight percentage of the photocurable coating is 3%, the weight percentage of the graded nano silver powder to the photocurable coating is 1%, and the weight ratio of the acrylic polyurethane resin to the photocurable coating is 96%.
本实施例的其余部分与实施例1相同，这里不再赘述。The rest of the embodiment is the same as that of Embodiment 1, and details are not described herein again.
实施例3。Example 3.
一种抗电磁辐射保护膜的制备方法，包括以下加工步骤：A method for preparing an anti-electromagnetic radiation protection film, comprising the following processing steps:
步骤一：具有抗电磁辐射功能的光固化涂料的制备Step 1: Preparation of photocurable coating with anti-electromagnetic radiation function
A、采用多壁/单壁碳纳米管利用50倍质量的浓硝酸在沸腾状态下加热回流处理，加热温度为160℃，对碳纳米管进行纯化与表面活化，反应时间为4.5h，然后过滤并用去离子水洗涤，得到处理后的碳纳米管；A. Multi-wall/single-walled carbon nanotubes are heated and refluxed under boiling conditions with 50 times of concentrated concentrated nitric acid. The heating temperature is 160 ° C. The carbon nanotubes are purified and surface activated for 4.5 h, then filtered. And washing with deionized water to obtain treated carbon nanotubes;
B、将处理后的碳纳米管与苯胺在酸性条件下混合形成预聚体，酸性条件为用HCl调节pH为1，碳纳米管与苯胺的质量比为1:60，然后滴加(NH4)2S2O8进行氧化聚合，(NH4)2S2O8与苯胺的摩尔比为1:1，得到碳纳米管-聚苯胺复合材料，过滤，洗涤，在真空条件下干燥20min，干燥温度为100℃，真空度为-90kPa；B. The treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer. The acidic condition is to adjust the pH to 1 with HCl, the mass ratio of carbon nanotubes to aniline is 1:60, and then dropwise (NH 4 ) 2 S 2 O 8 is subjected to oxidative polymerization, and the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1, and the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum for 20 minutes. Drying temperature is 100 ° C, vacuum degree is -90 kPa;
C、将碳纳米管-聚苯胺复合材料通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，搅拌速度为900转/min，分散时间是4.5h，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为4％；所述丙烯酸聚氨酯树脂为7官能度丙烯酸聚氨酯树脂；C. The carbon nanotube-polyaniline composite material is dispersed into the acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, the stirring speed is 900 rpm, the dispersion time is 4.5 h, centrifugal filtration, and the light curing with electromagnetic wave resistance is obtained. The coating, the carbon nanotube-polyaniline composite material accounts for 4% by weight of the photocurable coating; the acrylic urethane resin is a 7-functional acrylic polyurethane resin;
步骤二：将光固化涂料用微凹辊涂布在PET基材上，光固化涂料的涂布厚度5μm，微凹辊的直径为35mm，微凹辊的线数为80；所述PET基材的厚度为75μm，PET基材的透光率95％； Step 2: coating the photocurable coating on the PET substrate with a micro concave roll, the coating thickness of the photocurable coating is 5 μm, the diameter of the micro concave roller is 35 mm, and the number of lines of the micro concave roller is 80; the PET substrate The thickness of the film is 75 μm, and the transmittance of the PET substrate is 95%;
步骤三：涂料固化成膜Step 3: The coating is cured to form a film
将步骤二加工后的PET基材经导辊送达UV灯箱，导辊的输送速度为9m/min，UV灯的光强为600mj/cm2；The PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 9 m/min, and the light intensity of the UV lamp is 600 mj/cm 2 ;
步骤四：制备抗电磁辐射保护膜Step 4: Preparation of anti-electromagnetic radiation protection film
在步骤三加工后的PET基材的背面涂覆厚度为15μm的液态加成型反应硅胶，经过烘箱烘烤，烘烤温度为150℃，然后贴上PET护膜，所述PET护膜的厚度为30μm，PET护膜的透光率为92％，制得抗电磁辐射保护膜。On the back side of the PET substrate processed in the third step, a liquid addition reaction silica gel having a thickness of 15 μm is applied, baked in an oven, baked at a temperature of 150 ° C, and then a PET film is attached, and the thickness of the PET film is At 30 μm, the transmittance of the PET film was 92%, and an anti-electromagnetic radiation protection film was obtained.
本实施例的光固化涂料的固含量为42％，粘度为60cps，制得的抗电磁辐射保护膜透光率为90％。The photocurable coating of the present embodiment has a solid content of 42% and a viscosity of 60 cps, and the prepared electromagnetic radiation protection film has a light transmittance of 90%.
实施例4。Example 4.
本实施例与实施例3的不同之处在于：本实施例中，步骤一，C、所述光固化涂料还包括有重量百分比为2％的级配纳米银粉，级配纳米银粉包括200nm银粉和30nm银粉，200nm银粉和30nm银粉的质量比为1:7。The difference between the embodiment and the embodiment 3 is that, in the embodiment, the step 1, C, the photocurable coating further comprises a graded nano silver powder having a weight percentage of 2%, and the graded nano silver powder comprises 200 nm silver powder and The mass ratio of 30 nm silver powder, 200 nm silver powder and 30 nm silver powder is 1:7.
将碳纳米管-聚苯胺复合材料和级配纳米银粉通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为4％，级配纳米银粉占光固化涂料的重量百分比为2％，丙烯酸聚氨酯树脂占光固化涂料的重量百分比为94％。The carbon nanotube-polyaniline composite material and the graded nano silver powder were dispersed into acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having anti-electromagnetic wave effect, and the carbon nanotube-polyaniline composite material accounted for The weight percentage of the photocurable coating was 4%, the weight percentage of the graded nanosilver powder to the photocurable coating was 2%, and the weight ratio of the acrylic polyurethane resin to the photocurable coating was 94%.
本实施例的其余部分与实施例3相同，这里不再赘述。The rest of the embodiment is the same as that of Embodiment 3, and details are not described herein again.
实施例5。Example 5.
一种抗电磁辐射保护膜的制备方法，包括以下加工步骤：A method for preparing an anti-electromagnetic radiation protection film, comprising the following processing steps:
步骤一：具有抗电磁辐射功能的光固化涂料的制备Step 1: Preparation of photocurable coating with anti-electromagnetic radiation function
A、采用多壁/单壁碳纳米管利用60倍质量的浓硝酸在沸腾状态下加热回流处理，加热温度为170℃，对碳纳米管进行纯化与表面活化，反应时间为4h，然后过滤并用去离子水洗涤，得到处理后的碳纳米管；A. Multi-wall/single-walled carbon nanotubes are heated and refluxed in boiling state with 60 times of concentrated concentrated nitric acid. The heating temperature is 170 ° C, and the carbon nanotubes are purified and surface activated for 4 hours, then filtered and used. Washing with deionized water to obtain treated carbon nanotubes;
B、将处理后的碳纳米管与苯胺在酸性条件下混合形成预聚体，酸性条件为用HCl调节pH为1.5，碳纳米管与苯胺的质量比为1:70，然后滴加(NH4)2S2O8进行氧化聚合，(NH4)2S2O8与苯胺的摩尔比为1:1，得到碳纳米管-聚苯胺复合材料，过滤，洗涤，在真空条件下干燥30min，干燥温度为100℃，真空度为 -85kPa；B. The treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer. The acidic condition is to adjust the pH to 1.5 with HCl, the mass ratio of carbon nanotubes to aniline is 1:70, and then dropwise (NH 4 ) 2 S 2 O 8 is subjected to oxidative polymerization, and the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1, and the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum for 30 minutes. Drying temperature is 100 ° C, vacuum degree is -85 kPa;
C、将碳纳米管-聚苯胺复合材料通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，搅拌速度为1000转/min，分散时间是4h，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为5％；所述丙烯酸聚氨酯树脂为8官能度丙烯酸聚氨酯树脂；C. The carbon nanotube-polyaniline composite material is dispersed into the acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, the stirring speed is 1000 rpm, the dispersion time is 4 h, centrifugal filtration, and the photocurable coating with anti-electromagnetic effect is obtained. The carbon nanotube-polyaniline composite material accounts for 5% by weight of the photocurable coating; the acrylic urethane resin is an 8-functional acrylic polyurethane resin;
步骤二：将光固化涂料用微凹辊涂布在PET基材上，光固化涂料的涂布厚度6μm，微凹辊的直径为40mm，微凹辊的线数为150；所述PET基材的厚度为100μm，PET基材的透光率96％；Step 2: coating the photocurable coating on the PET substrate with a micro concave roll, the coating thickness of the photocurable coating is 6 μm, the diameter of the micro concave roller is 40 mm, and the number of lines of the micro concave roller is 150; the PET substrate The thickness of the film is 100 μm, and the transmittance of the PET substrate is 96%;
步骤三：涂料固化成膜Step 3: The coating is cured to form a film
将步骤二加工后的PET基材经导辊送达UV灯箱，导辊的输送速度为10m/min，UV灯的光强为500mj/cm2；The PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 10 m/min, and the light intensity of the UV lamp is 500 mj/cm 2 ;
步骤四：制备抗电磁辐射保护膜Step 4: Preparation of anti-electromagnetic radiation protection film
在步骤三加工后的PET基材的背面涂覆厚度为20μm的液态亚克力胶水，经过烘箱烘烤，烘烤温度为160℃，然后贴上PET护膜，所述PET护膜的厚度为50μm，PET护膜的透光率为93％，制得抗电磁辐射保护膜。The back surface of the processed PET substrate is coated with a liquid acrylic glue having a thickness of 20 μm, baked in an oven, baked at a temperature of 160 ° C, and then attached with a PET film having a thickness of 50 μm. The transmittance of the PET film is 93%, and an anti-electromagnetic radiation protection film is obtained.
本实施例的光固化涂料的固含量为45％，粘度为70cps，制得的抗电磁辐射保护膜透光率为91％。The photocurable coating of the present embodiment has a solid content of 45% and a viscosity of 70 cps, and the prepared electromagnetic radiation protection film has a light transmittance of 91%.
实施例6。Example 6.
本实施例与实施例5的不同之处在于：本实施例中，步骤一，C、所述光固化涂料还包括有重量百分比为3％的级配纳米银粉，级配纳米银粉包括200nm银粉和30nm银粉，200nm银粉和30nm银粉的质量比为1:7。The difference between this embodiment and the embodiment 5 is that, in the embodiment, the step 1, C, the photocurable coating further comprises a grading nano silver powder in a weight percentage of 3%, and the grading nano silver powder comprises 200 nm silver powder and The mass ratio of 30 nm silver powder, 200 nm silver powder and 30 nm silver powder is 1:7.
将碳纳米管-聚苯胺复合材料和级配纳米银粉通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为5％，级配纳米银粉占光固化涂料的重量百分比为3％，丙烯酸聚氨酯树脂占光固化涂料的重量百分比为92％。The carbon nanotube-polyaniline composite material and the graded nano silver powder were dispersed into acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having anti-electromagnetic wave effect, and the carbon nanotube-polyaniline composite material accounted for The weight percentage of the photocurable coating was 5%, the weight percentage of the graded nanosilver powder to the photocurable coating was 3%, and the weight ratio of the acrylic polyurethane resin to the photocurable coating was 92%.
本实施例的其余部分与实施例5相同，这里不再赘述。The rest of the embodiment is the same as that of the embodiment 5, and details are not described herein again.
实施例7。Example 7.
一种抗电磁辐射保护膜的制备方法，包括以下加工步骤： A method for preparing an anti-electromagnetic radiation protection film, comprising the following processing steps:
步骤一：具有抗电磁辐射功能的光固化涂料的制备Step 1: Preparation of photocurable coating with anti-electromagnetic radiation function
A、采用多壁/单壁碳纳米管利用70倍质量的浓硝酸在沸腾状态下加热回流处理，加热温度为180℃，对碳纳米管进行纯化与表面活化，反应时间为3h，然后过滤并用去离子水洗涤，得到处理后的碳纳米管；A. Multi-wall/single-walled carbon nanotubes are heated and refluxed in boiling state with 70 times of concentrated concentrated nitric acid. The heating temperature is 180 ° C. The carbon nanotubes are purified and surface activated for 3 hours, then filtered and used. Washing with deionized water to obtain treated carbon nanotubes;
B、将处理后的碳纳米管与苯胺在酸性条件下混合形成预聚体，酸性条件为用HCl调节pH为2，碳纳米管与苯胺的质量比为1:80，然后滴加(NH4)2S2O8进行氧化聚合，(NH4)2S2O8与苯胺的摩尔比为1:1.1，得到碳纳米管-聚苯胺复合材料，过滤，洗涤，在真空条件下干燥30min，干燥温度为100℃，真空度为-80kPa；B. The treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer. The acidic condition is to adjust the pH to 2 with HCl, the mass ratio of carbon nanotubes to aniline is 1:80, and then dropwise (NH 4 ) 2 S 2 O 8 is oxidatively polymerized, the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1.1, the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum for 30 min. Drying temperature is 100 ° C, vacuum degree is -80 kPa;
C、将碳纳米管-聚苯胺复合材料通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，搅拌速度为1100转/min，分散时间是3.5h，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为6％；所述丙烯酸聚氨酯树脂为9官能度丙烯酸聚氨酯树脂；C. The carbon nanotube-polyaniline composite material is dispersed into the acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, the stirring speed is 1100 rpm, the dispersion time is 3.5 h, centrifugal filtration, and the light curing with electromagnetic wave resistance is obtained. The coating, the carbon nanotube-polyaniline composite material accounts for 6% by weight of the photocurable coating; the acrylic urethane resin is a 9-functional acrylic polyurethane resin;
步骤二：将光固化涂料用微凹辊涂布在PET基材上，光固化涂料的涂布厚度8μm，微凹辊的直径为45mm，微凹辊的线数为200；所述PET基材的厚度为150μm，PET基材的透光率96％；Step 2: coating the photocurable coating on the PET substrate with a micro concave roll, the coating thickness of the photocurable coating is 8 μm, the diameter of the micro concave roller is 45 mm, and the number of lines of the micro concave roller is 200; the PET substrate The thickness of the film is 150 μm, and the transmittance of the PET substrate is 96%;
步骤三：涂料固化成膜Step 3: The coating is cured to form a film
将步骤二加工后的PET基材经导辊送达UV灯箱，导辊的输送速度为12m/min，UV灯的光强为350mj/cm2；The PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 12 m/min, and the light intensity of the UV lamp is 350 mj/cm 2 ;
步骤四：制备抗电磁辐射保护膜Step 4: Preparation of anti-electromagnetic radiation protection film
在步骤三加工后的PET基材的背面涂覆厚度为25μm的液态亚克力胶水，经过烘箱烘烤，烘烤温度为180℃，然后贴上PET护膜，所述PET护膜的厚度为60μm，PET护膜的透光率为94％，制得抗电磁辐射保护膜。On the back side of the PET substrate processed in the third step, a liquid acrylic glue having a thickness of 25 μm is applied, baked in an oven, baked at a temperature of 180 ° C, and then a PET film is attached, and the thickness of the PET film is 60 μm. The transmittance of the PET film is 94%, and an anti-electromagnetic radiation protection film is obtained.
本实施例的光固化涂料的固含量为48％，粘度为80cps，制得的抗电磁辐射保护膜透光率为92％。The photocurable coating of the present embodiment has a solid content of 48% and a viscosity of 80 cps, and the prepared electromagnetic radiation protection film has a light transmittance of 92%.
实施例8。Example 8.
本实施例与实施例7的不同之处在于：本实施例中，步骤一，C、所述光固化涂料还包括有重量百分比为4％的级配纳米银粉，级配纳米银粉包括200nm银粉和30nm银粉，200nm银粉和30nm银粉的质量比为1:7。 The difference between this embodiment and the embodiment 7 is that, in the embodiment, the step 1, C, the photocurable coating further comprises a graded nano silver powder having a weight percentage of 4%, and the graded nano silver powder comprises 200 nm silver powder and The mass ratio of 30 nm silver powder, 200 nm silver powder and 30 nm silver powder is 1:7.
将碳纳米管-聚苯胺复合材料和级配纳米银粉通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为6％，级配纳米银粉占光固化涂料的重量百分比为4％，丙烯酸聚氨酯树脂占光固化涂料的重量百分比为90％。The carbon nanotube-polyaniline composite material and the graded nano silver powder were dispersed into acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having anti-electromagnetic wave effect, and the carbon nanotube-polyaniline composite material accounted for The weight percentage of the photocurable coating is 6%, the weight percentage of the graded nano silver powder to the photocurable coating is 4%, and the weight ratio of the acrylic polyurethane resin to the photocurable coating is 90%.
本实施例的其余部分与实施例7相同，这里不再赘述。The rest of the embodiment is the same as that of Embodiment 7, and details are not described herein again.
实施例9。Example 9.
一种抗电磁辐射保护膜的制备方法，包括以下加工步骤：A method for preparing an anti-electromagnetic radiation protection film, comprising the following processing steps:
步骤一：具有抗电磁辐射功能的光固化涂料的制备Step 1: Preparation of photocurable coating with anti-electromagnetic radiation function
A、采用多壁/单壁碳纳米管利用80倍质量的浓硝酸在沸腾状态下加热回流处理，加热温度为150℃，对碳纳米管进行纯化与表面活化，反应时间为2h，然后过滤并用去离子水洗涤，得到处理后的碳纳米管；A. Multi-wall/single-walled carbon nanotubes are heated and refluxed in boiling state with 80 times of concentrated concentrated nitric acid. The heating temperature is 150 ° C. The carbon nanotubes are purified and surface activated for 2 hours, then filtered and used. Washing with deionized water to obtain treated carbon nanotubes;
B、将处理后的碳纳米管与苯胺在酸性条件下混合形成预聚体，酸性条件为用HCl调节pH为2，碳纳米管与苯胺的质量比为1:100，然后滴加(NH4)2S2O8进行氧化聚合，(NH4)2S2O8与苯胺的摩尔比为1:1.2，得到碳纳米管-聚苯胺复合材料，过滤，洗涤，在真空条件下干燥40min，干燥温度为100℃，真空度为-75kPa；B. The treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer. The acidic condition is to adjust the pH to 2 with HCl, the mass ratio of carbon nanotubes to aniline is 1:100, and then dropwise (NH 4 ) 2 S 2 O 8 is subjected to oxidative polymerization, and the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1.2, and the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum for 40 min. Drying temperature is 100 ° C, vacuum degree is -75 kPa;
C、将碳纳米管-聚苯胺复合材料通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，搅拌速度为1300转/min，分散时间是3h，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为8％；所述丙烯酸聚氨酯树脂为9官能度丙烯酸聚氨酯树脂；C. The carbon nanotube-polyaniline composite material is dispersed into the acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, the stirring speed is 1300 rpm, the dispersion time is 3 h, centrifugal filtration, and the photocurable coating with anti-electromagnetic effect is obtained. The carbon nanotube-polyaniline composite material accounts for 8% by weight of the photocurable coating; the acrylic urethane resin is a 9-functional acrylic polyurethane resin;
步骤二：将光固化涂料用微凹辊涂布在PET基材上，光固化涂料的涂布厚度10μm，微凹辊的直径为50mm，微凹辊的线数为400；所述PET基材的厚度为200μm，PET基材的透光率95％；Step 2: coating the photocurable coating on the PET substrate with a micro concave roll, the coating thickness of the photocurable coating is 10 μm, the diameter of the micro concave roller is 50 mm, and the number of lines of the micro concave roller is 400; the PET substrate The thickness of the film is 200 μm, and the transmittance of the PET substrate is 95%;
步骤三：涂料固化成膜Step 3: The coating is cured to form a film
将步骤二加工后的PET基材经导辊送达UV灯箱，导辊的输送速度为13m/min，UV灯的光强为200mj/cm2；The PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 13 m/min, and the light intensity of the UV lamp is 200 mj/cm 2 ;
步骤四：制备抗电磁辐射保护膜Step 4: Preparation of anti-electromagnetic radiation protection film
在步骤三加工后的PET基材的背面涂覆厚度为30μm的聚氨酯胶水，经过 烘箱烘烤，烘烤温度为200℃，然后贴上PET护膜，所述PET护膜的厚度为75μm，PET护膜的透光率为95％，制得抗电磁辐射保护膜。On the back side of the PET substrate processed in the third step, a polyurethane glue having a thickness of 30 μm is applied. The oven was baked at a baking temperature of 200 ° C, and then a PET film was attached. The thickness of the PET film was 75 μm, and the transmittance of the PET film was 95% to obtain an anti-electromagnetic radiation protection film.
本实施例的光固化涂料的固含量为50％，粘度为100cps，制得的抗电磁辐射保护膜透光率为93％。The photocurable coating of the present embodiment has a solid content of 50% and a viscosity of 100 cps, and the prepared electromagnetic radiation protection film has a light transmittance of 93%.
实施例10。Example 10.
本实施例与实施例9的不同之处在于：本实施例中，步骤一，C、所述光固化涂料还包括有重量百分比为5％的级配纳米银粉，级配纳米银粉包括200nm银粉和30nm银粉，200nm银粉和30nm银粉的质量比为1:7。The present embodiment is different from the embodiment 9 in that, in the embodiment, the step 1, C, the photocurable coating further comprises a 5% by weight of gradation nano silver powder, and the grading nano silver powder comprises 200 nm silver powder and The mass ratio of 30 nm silver powder, 200 nm silver powder and 30 nm silver powder is 1:7.
将碳纳米管-聚苯胺复合材料和级配纳米银粉通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为8％，级配纳米银粉占光固化涂料的重量百分比为5％，丙烯酸聚氨酯树脂占光固化涂料的重量百分比为87％。The carbon nanotube-polyaniline composite material and the graded nano silver powder were dispersed into acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having anti-electromagnetic wave effect, and the carbon nanotube-polyaniline composite material accounted for The weight percentage of the photocurable coating is 8%, the weight percentage of the graded nano silver powder to the photocurable coating is 5%, and the weight ratio of the acrylic polyurethane resin to the photocurable coating is 87%.
本实施例的其余部分与实施例9相同，这里不再赘述。The rest of the embodiment is the same as that of Embodiment 9, and details are not described herein again.
实施例1-10制得的抗电磁辐射保护膜的物理特性如下表所示。The physical properties of the anti-electromagnetic radiation protective film prepared in Examples 1-10 are shown in the following table.
Figure PCTCN2015079843-appb-000001
Figure PCTCN2015079843-appb-000001
以上所述实施方式，只是本发明的较佳实施方式，并非来限制本发明实施范围，故凡依本发明申请专利范围所述的构造、特征及原理所做的等效变化或修饰，均应包括本发明专利申请范围内。 The above-described embodiments are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Therefore, equivalent changes or modifications made by the structures, features, and principles described in the claims of the present invention should be It is included in the scope of the patent application of the present invention.

Claims (10)

  1. 一种抗电磁辐射保护膜的制备方法，其特征在于：包括以下加工步骤：A method for preparing an anti-electromagnetic radiation protection film, comprising: the following processing steps:
    步骤一：具有抗电磁辐射功能的光固化涂料的制备Step 1: Preparation of photocurable coating with anti-electromagnetic radiation function
    A、采用多壁/单壁碳纳米管利用40-80倍质量的浓硝酸在沸腾状态下加热回流处理，对碳纳米管进行纯化与表面活化，反应时间为2-5h，然后过滤并用去离子水洗涤，得到处理后的碳纳米管；A. Multi-wall/single-walled carbon nanotubes are heated and refluxed in boiling state with 40-80 times of concentrated concentrated nitric acid. The carbon nanotubes are purified and surface-activated for 2-5 hours, then filtered and deionized. Washing with water to obtain treated carbon nanotubes;
    B、将处理后的碳纳米管与苯胺在酸性条件下混合形成预聚体，碳纳米管与苯胺的质量比为1:50-1:100，然后滴加(NH4)2S2O8进行氧化聚合，(NH4)2S2O8与苯胺的摩尔比为1:1-1:1.2，得到碳纳米管-聚苯胺复合材料，过滤，洗涤，在真空条件下干燥；B. The treated carbon nanotubes are mixed with aniline under acidic conditions to form a prepolymer. The mass ratio of carbon nanotubes to aniline is 1:50-1:100, and then (NH 4 ) 2 S 2 O 8 is added dropwise. The oxidative polymerization is carried out, and the molar ratio of (NH 4 ) 2 S 2 O 8 to aniline is 1:1 to 1:1.2, and the carbon nanotube-polyaniline composite material is obtained, filtered, washed, and dried under vacuum;
    C、将碳纳米管-聚苯胺复合材料通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为3-8％；C. The carbon nanotube-polyaniline composite material is dispersed into an acrylic urethane resin by high-speed stirring and ultrasonic dispersing equipment, and centrifugally filtered to obtain a photocurable coating having an electromagnetic wave resistance effect, and the carbon nanotube-polyaniline composite material occupies the photocurable coating material. The weight percentage is 3-8%;
    步骤二：将光固化涂料用微凹辊涂布在PET基材上，光固化涂料的涂布厚度3-10μm；Step 2: coating the photocurable coating on the PET substrate with a micro concave roll, the coating thickness of the photocurable coating is 3-10 μm;
    步骤三：涂料固化成膜Step 3: The coating is cured to form a film
    将步骤二加工后的PET基材经导辊送达UV灯箱，导辊的输送速度为8-13m/min，UV灯的光强为200-800mj/cm2；The PET substrate processed in the second step is sent to the UV light box through a guide roller, the conveying speed of the guiding roller is 8-13 m/min, and the light intensity of the UV lamp is 200-800 mj/cm 2 ;
    步骤四：制备抗电磁辐射保护膜Step 4: Preparation of anti-electromagnetic radiation protection film
    在步骤三加工后的PET基材的背面涂覆厚度为10-30μm的液态加成型反应硅胶、液态亚克力胶水或聚氨酯胶水，经过烘箱烘烤，烘烤温度为130-200℃，然后贴上PET护膜，制得抗电磁辐射保护膜。The back surface of the PET substrate processed in the third step is coated with a liquid addition reaction silica gel, a liquid acrylic glue or a polyurethane glue having a thickness of 10-30 μm, baked in an oven, baked at a temperature of 130-200 ° C, and then affixed with PET. The film is protected against electromagnetic radiation.
  2. 根据权利要求1所述的一种抗电磁辐射保护膜的制备方法，其特征在于：所述步骤一中，A、多壁/单壁碳纳米管和浓硝酸的加热回流处理中，加热温度为150-180℃；B、酸性条件，具体为用HCl调节pH为1-2；C、高速搅拌设备的搅拌速度为800-1300转/min，超声波分散设备的分散时间是3-5h。The method for preparing an anti-electromagnetic radiation protection film according to claim 1, wherein in the step 1, the heating temperature of the A, the multi-wall/single-walled carbon nanotubes and the concentrated nitric acid is heated and refluxed. 150-180 ° C; B, acidic conditions, specifically to adjust the pH to 1-2 with HCl; C, high-speed stirring equipment stirring speed of 800-1300 rev / min, ultrasonic dispersion equipment dispersion time is 3-5h.
  3. 根据权利要求1所述的一种抗电磁辐射保护膜的制备方法，其特征在于：所述步骤一中，B、碳纳米管与苯胺的质量比为1:60-1:80，真空条件下干燥20-40min，干燥温度为100℃，真空度为-75kPa到-100kPa。 The method for preparing an anti-electromagnetic radiation protection film according to claim 1, wherein in the first step, the mass ratio of B, carbon nanotubes and aniline is 1:60-1:80, under vacuum condition Dry for 20-40 min, dry at 100 ° C, and vacuum from -75 kPa to -100 kPa.
  4. 根据权利要求1所述的一种抗电磁辐射保护膜的制备方法，其特征在于：所述步骤一中，C、所述丙烯酸聚氨酯树脂为6-9官能度丙烯酸聚氨酯树脂。The method for preparing an anti-electromagnetic radiation protection film according to claim 1, wherein in the first step, C, the acrylic urethane resin is a 6-9-functional acrylic urethane resin.
  5. 根据权利要求1所述的一种抗电磁辐射保护膜的制备方法，其特征在于：所述步骤一中，C、所述光固化涂料还包括有重量百分比为1-5％的级配纳米银粉，级配纳米银粉包括200nm银粉和30nm银粉，200nm银粉和30nm银粉的质量比为1:7。The method for preparing an anti-electromagnetic radiation protection film according to claim 1, wherein in the step 1, C, the photocurable coating further comprises grading nano silver powder in a weight percentage of 1-5%. The graded nano silver powder comprises 200 nm silver powder and 30 nm silver powder, and the mass ratio of 200 nm silver powder to 30 nm silver powder is 1:7.
  6. 根据权利要求5所述的一种抗电磁辐射保护膜的制备方法，其特征在于：所述步骤一中，C、将碳纳米管-聚苯胺复合材料和级配纳米银粉通过高速搅拌和超声波分散设备分散到丙烯酸聚氨酯树脂中，离心过滤，得到具有抗电磁波效果的光固化涂料，碳纳米管-聚苯胺复合材料占光固化涂料的重量百分比为3-8％，级配纳米银粉占光固化涂料的重量百分比为1-5％，丙烯酸聚氨酯树脂占光固化涂料的重量百分比为87-96％。The method for preparing an anti-electromagnetic radiation protection film according to claim 5, wherein in the first step, C, the carbon nanotube-polyaniline composite material and the graded nano silver powder are dispersed by high speed stirring and ultrasonic wave. The device is dispersed in an acrylic urethane resin and centrifugally filtered to obtain a photocurable coating having an anti-electromagnetic effect. The carbon nanotube-polyaniline composite material accounts for 3-8% by weight of the photocurable coating, and the gradation of the nano silver powder occupies the photocurable coating. The weight percentage is 1-5%, and the acrylic polyurethane resin accounts for 87-96% by weight of the photocurable coating.
  7. 根据权利要求1所述的一种抗电磁辐射保护膜的制备方法，其特征在于：所述步骤二中，微凹辊的直径为30-50mm，微凹辊的线数为40-400。The method for preparing an anti-electromagnetic radiation protection film according to claim 1, wherein in the second step, the diameter of the micro concave roller is 30-50 mm, and the number of lines of the micro concave roller is 40-400.
  8. 根据权利要求1所述的一种抗电磁辐射保护膜的制备方法，其特征在于：所述步骤一中，制得的光固化涂料的固含量为40-50％，粘度为50-100cps。The method for preparing an anti-electromagnetic radiation protection film according to claim 1, wherein in the first step, the photocurable coating has a solid content of 40-50% and a viscosity of 50-100 cps.
  9. 根据权利要求1所述的一种抗电磁辐射保护膜的制备方法，其特征在于：所述PET基材的厚度为25-200μm，PET基材的透光率不小于95％，所述PET护膜的厚度为25-75μm，PET护膜的透光率为92-95％。The method for preparing an anti-electromagnetic radiation protection film according to claim 1, wherein the PET substrate has a thickness of 25-200 μm, and the transmittance of the PET substrate is not less than 95%. The thickness of the film is 25-75 μm, and the transmittance of the PET film is 92-95%.
  10. 一种抗电磁辐射保护膜，其特征在于：如权利要求1-7中任意一项所述的一种抗电磁辐射保护膜的制备方法制得的抗电磁辐射保护膜，抗电磁辐射保护膜的透光率为90-93％。 An anti-electromagnetic radiation protection film, which is an anti-electromagnetic radiation protection film prepared by the method for preparing an anti-electromagnetic radiation protection film according to any one of claims 1 to 7, which is resistant to electromagnetic radiation protection film. The light transmittance is 90-93%.
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