CN115850803A - Antifogging and antidazzling hardened film - Google Patents
Antifogging and antidazzling hardened film Download PDFInfo
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- CN115850803A CN115850803A CN202211498137.5A CN202211498137A CN115850803A CN 115850803 A CN115850803 A CN 115850803A CN 202211498137 A CN202211498137 A CN 202211498137A CN 115850803 A CN115850803 A CN 115850803A
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Abstract
An antifogging and antiglare hardened film, which consists of a transparent support and two layers of antiglare hardened coatings coated on one side of the transparent support; the first anti-glare hardened coating is obtained by coating and curing coating liquid prepared from the following components in parts by mass: thermosetting resin: 30 to 45 percent; UV curing resin: 1.5 to 3.5; photoinitiator (2): 0.08 to 0.3; thermal curing agent: 0.9 to 4.0; first organic particles: 2.9 to 6.2; leveling agent: 1.0 to 2.5; solvent: 38.9 to 63.62; the second anti-dazzle hardening coating is formed by coating and curing a coating liquid prepared from the following components in parts by mass: UV curing resin: 35 to 55 percent; photoinitiator (2): 1.5 to 6; leveling agent: 0.8 to 1.8; wetting and dispersing agent: 0.5 to 1.7; second organic particles: 0.7 to 3.25; zinc oxide nanoparticles: 0.35 to 1.2; solvent: 33.35 to 61.15. The hardened film has the technical characteristics of excellent antifogging property, high definition, high gloss and low roughness, and also has a certain ultraviolet blocking effect.
Description
Technical Field
The invention relates to a hardened film, in particular to an anti-fog and anti-glare hardened film, and belongs to the technical field of thin films.
Background
The anti-glare hardened film can play a basic protection role on a display device, and can also perform diffuse reflection on incident strong light by utilizing the concave-convex microstructures on the surface of the anti-glare hardened film, so that the anti-glare effect is achieved, and the image viewing effect is improved.
At present, an anti-glare protective film for a display usually adopts a mode of adding organic or inorganic particles into a coating based on resin to form an uneven microstructure on the surface of a coating, so that a diffuse reflection effect is achieved on incident light, and an anti-glare function is realized. In practical production and application, on one hand, coating and film covering treatment needs to be carried out on the basis of the hardening film so as to carry out the next process. However, the surface roughness is generated by the particles, and simultaneously, the surface glossiness is reduced, and the difficulty of film coating and film covering is increased due to the improvement of the roughness; on the other hand, display devices, particularly for outdoor equipment, need to be adapted to weather factors, and need to maintain workability in extreme weather, i.e., need to have some antifogging property.
Disclosure of Invention
The invention provides an anti-fog and anti-glare hardened film for overcoming the defects of the prior art, which is characterized in that a support body is coated with two layers of anti-glare coatings, organic particles are added into the coatings, the particle size and the coating thickness of the organic particles are controlled, and triangular prism-shaped zinc oxide nanoparticles are added into a second coating, so that the anti-fog and anti-glare hardened film has the advantages of high definition, high glossiness and low roughness.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an antifogging antiglare hardened film, said hardened film consisting of a transparent support and two layers of antiglare hardened coatings coated on one side of the transparent support;
the first anti-glare hardened coating is obtained by coating and curing a coating liquid prepared from the following components in parts by mass: thermosetting resin: 30 to 45 percent;
UV curing resin: 1.5 to 3.5;
photoinitiator (2): 0.08 to 0.3;
thermal curing agent: 0.9 to 4.0;
first organic particles: 2.9 to 6.2;
leveling agent: 1.0 to 2.5;
solvent: 38.9 to 63.62;
the second anti-glare hardened coating is formed by coating and curing a coating liquid prepared from the following components in parts by mass: UV curing resin: 35 to 55 percent;
photoinitiator (2): 1.5 to 6;
leveling agent: 0.8 to 1.8;
wetting and dispersing agent: 0.5 to 1.7;
second organic particles: 0.7 to 3.25;
zinc oxide nanoparticles: 0.35 to 1.2;
solvent: 33.35 to 61.15.
The antifogging and antiglare hardened film has a particle size of the first organic particles of D1=5 to 12 μm, and a particle size of the second organic particles of D2=2 to 8 μm, and both of the first organic particles and the second organic particles are monodisperse organic particles; the first anti-glare hardened coating has a thickness L1, the second anti-glare hardened coating has a thickness L2, and L1, L2, D1 and D2 satisfy the following relations: D1-L1 is more than 0 and less than L2, and D2+ D1-L1 is more than L2.
The anti-fog and anti-glare hardened film is characterized in that the zinc oxide nanoparticles are triangular prisms, and the particle size is 50-120 nm.
The anti-fog anti-glare hardened film is prepared from the zinc oxide nanoparticles by a microemulsion method, and comprises the following preparation steps:
a. preparation of a cyclohexane-water-in-oil emulsion: adding 40mL of cyclohexane and 1.5mL of emulsifier polyglycerol ricinoleate into a flask, and magnetically stirring and dispersing to obtain a cyclohexane oil phase; adding 2mL of deionized water and azo isobutyl cyano formamide into a beaker, uniformly mixing, adding a small amount of NaOH, and adjusting the pH value to 6-8 to obtain a water phase; slowly adding the water phase into a flask filled with the oil phase, and rapidly stirring and emulsifying at room temperature for 30min to obtain uniform and stable cyclohexane-water-in-oil emulsion; the head groups (ether groups and alcohol groups) in the emulsifier polyglycerol ricinoleate are concentrated at an oil-water interface;
b. preparation of isopropanol methyl zinc precursor: adding 7.8g of ZnCl 2 Pouring into a three-neck flask, and adding SOCl 2 ZnCl treated by reflux drying 2 The residual SOCl in the flask was then removed in vacuo 2 20.7gCH 3 n-Bu of MgI 2 Slowly dripping the O solution into a flask, stirring vigorously, cooling and refluxing for 50 hours at 70 ℃, distilling at 130-160 ℃ to obtain dimethyl zinc, dissolving the obtained dimethyl zinc in a toluene solvent, dripping 3.5g of ethanol, stirring the solution at room temperature for 12 hours, drying in vacuum to remove toluene to obtain a white solid, and washing and drying with cyclohexane to obtain an isopropanol methyl zinc precursor;
c. forming zinc oxide nano particles: dissolving an isopropanol methyl zinc precursor in an ethanol solvent, after the isopropanol methyl zinc precursor is fully dissolved, slowly dropwise adding the isopropanol methyl zinc precursor into a cyclohexane-water-in-oil emulsion, when the concentration of the isopropanol methyl zinc precursor in a cyclohexane oil phase reaches saturation, diffusing the isopropanol methyl zinc precursor to an oil-water interface to form zinc oxide nano particles, and obtaining a triangular prism crystal structure under the action of different coordinated oxygen of ether groups and alcohol groups;
d. centrifugally dispersing the water layer and the oil layer, and filtering the water layer to obtain the zinc oxide nano-particles.
In the anti-fog and anti-glare hardened film, the first organic particles are one of butyl methacrylate, polymethyl methacrylate, methyl methacrylate or polybutyl methacrylate; the second organic particles are one of polymethacrylic acid, polybutylmethacrylate, methylmethacrylate or polymethylmethacrylate.
According to the anti-fog anti-glare hardened film, the thermosetting resin used in the first anti-glare hardened coating is polyurethane, the molecular weight of the thermosetting resin is 1000-6000, the UV curing resin is polyurethane acrylate, and the functionality of the UV curing resin is 6-9; the quality of the UV curing resin is not higher than 8% of that of the thermosetting resin, and the first anti-dazzle hardening coating is subjected to thermosetting at 100-120 ℃ for 2-5 min, so that the thermosetting resin is completely cured.
According to the anti-fog and anti-glare hardened film, the UV curing resin in the second anti-glare hardened coating is polyurethane acrylate with the functionality of 6-9.
In the anti-fog and anti-glare hardened film, the leveling agent in the first anti-glare hardened coating is an acrylic leveling agent; and the flatting agent in the second anti-dazzle hardening coating is an organic silicon flatting agent.
The transparent support is one of a triacetate fiber film (TAC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA) or Polyimide (PI), and the thickness of the transparent support is 40-125 mu m.
The first anti-glare hard-coating layer and the second anti-glare hard-coating layer are coated in one of a roll coating mode, a scraper coating mode, a bar coating mode and a gravure coating mode.
The invention has the beneficial effects that:
1. the invention relates to an anti-fog and anti-glare hardened film, which structurally comprises a transparent support and two layers of anti-glare coatings, wherein the thickness of the coatings and the particle diameters of the particles are controlled to meet the following requirements: D1-L1 is more than 0 and less than L2, and D2+ D1-L1 is more than L2, so that the first organic particles provide steps for the second organic particles in the second coating, and on one hand, the uniform arrangement of the second organic particles is facilitated, the surface roughness is reduced, and the glossiness is improved; on the other hand, under the same haze requirement, the required particle size is smaller, so that the definition of the anti-dazzle hardened film is improved, and the picture quality is improved.
2. The anti-fog and anti-dazzle hardened film has the advantages that the surface of the anti-fog and anti-dazzle hardened film is distributed with convex organic particles and nano zinc oxide particles, wherein the zinc oxide particles are in the shape of triangular prism, dense sharp corners are formed on the surface of the coating, a super-hydrophilic surface is formed, water cannot form water drops on the surface of the coating, and therefore the anti-fog effect is effectively achieved.
3. The anti-fog anti-glare hardened film is a direct contact interface of a user, needs better wear resistance and hardness, ensures the wear resistance and hardness of the coating by establishing a double coating while improving the surface by using the second organic particles with smaller particle size and simultaneously ensuring the coating thickness.
Drawings
FIG. 1 is a schematic structural view of an antifogging and antiglare hard-coating film of the present invention.
In the figure: 1. zinc oxide nanoparticles; 2. second organic particles; 3. a second anti-glare hardened coating; 4. first organic particles; 5. a first anti-glare hardened coating; 6. a transparent support.
Detailed Description
In order to solve the existing problems of the anti-dazzle hardened film, the anti-fog anti-dazzle hardened film provided by the invention uses two anti-dazzle layers, and the improved anti-fog anti-dazzle hardened film is obtained by controlling the thickness of the coating and the particle size of organic anti-dazzle particles in the coating.
Referring to fig. 1, the second anti-glare hardened coating is coated on the surface of the first anti-glare hardened coating, the thickness of the first anti-glare hardened coating and the particle size of the first organic particles are controlled to satisfy D1 > L1, and the part of the first organic particles in the first anti-glare hardened coating, which exceeds the thickness of the coating, can provide a certain height for the second anti-glare hardened coating to act as a step, so that the second organic particles are in direct contact with the step established by the first organic particles in the first anti-glare hardened coating, thereby controlling the protrusion height of the second organic particles and achieving the technical effects of high glossiness and low roughness. The resin in the first anti-glare hardened coating can increase the total coating thickness and ensure the effects of hardness of a hardened film and the like, wherein the UV-cured resin and the UV-cured resin in the second anti-glare hardened coating perform light curing together to enhance the tightness of the first anti-glare hardened coating and the second anti-glare hardened coating.
According to the invention, the zinc oxide nanoparticles added in the second anti-dazzle hardening coating are distributed on the surface of the coating to form dense sharp corners on the coating, so that a super-hydrophilic surface is formed, the surface tension of water is increased, and the anti-fog effect is effectively achieved. The preparation method of the zinc oxide nanoparticles comprises the following steps:
a. preparation of water-in-oil emulsion (cyclohexane-water): adding 40mL of cyclohexane and 1.5mL of emulsifier polyglycerol ricinoleate into a flask, and magnetically stirring and dispersing to obtain a cyclohexane oil phase; adding 2mL of ionic water and azo isobutyl cyano formamide into a beaker, uniformly mixing, adding a small amount of NaOH, and adjusting the pH value to 6-8 to obtain a water phase. Slowly adding the water phase into a flask filled with the oil phase, and performing ultrasonic treatment and emulsification for 30min at room temperature to obtain uniform and stable cyclohexane-water-in-oil emulsion. The head groups in the emulsifier polyglycerol ricinoleate are concentrated at the oil-water interface, such as ether groups and alcohol groups.
b. Preparation of isopropanol methyl zinc precursor: adding 7.8g of ZnCl 2 Pouring into a three-neck flask, and adding SOCl 2 ZnCl treated by reflux drying 2 The residual SOCl in the flask was then removed in vacuo 2 20.7gCH 3 n-Bu of MgI 2 Slowly dripping the O solution into a flask, stirring vigorously, cooling and refluxing at 70 ℃ for 50 hours, distilling at 130-160 ℃ to obtain dimethyl zinc, dissolving the obtained dimethyl zinc in a toluene solvent, dripping 3.5g of ethanol, stirring the solution at room temperature for 12 hours, drying in vacuum to remove toluene to obtain a white solid, washing with cyclohexane and drying to obtain the iso-zincPropanol methyl zinc precursor.
c. Formation of zinc oxide nanoparticles: dissolving an isopropanol methyl zinc precursor in cyclohexane, fully dispersing, slowly dropwise adding into emulsion, and when the concentration of the precursor in a cyclohexane oil phase reaches saturation, diffusing the precursor to an oil-water interface to form zinc oxide nanoparticles, and obtaining a triangular prism crystal structure under the action of different coordinated oxygen of ether groups and alcohol groups. Dispersing the water layer and the oil layer by centrifugation, and then filtering the water layer to obtain the zinc oxide nano-particles.
In the process of forming the zinc oxide nano particles, the precursor is diffused to a water phase from an oil phase and contacts with water at an oil-water interface for reaction, and an ether group and an alcohol group on the structure of the emulsifier polyglycerol polyricinoleate, which is gathered at the oil-water interface, have different crystal faces due to different types of two coordinated oxygen atoms, so that the anisotropic growth of crystals is controlled, and the triangular prism nano zinc oxide crystals are obtained.
In the invention, the curing mode of the first anti-glare hardened coating is thermal curing, the curing temperature is 100-120 ℃, the time is 2-5 min, the first anti-glare hardened coating is cured thermally, after cooling, the second anti-glare hardened coating is coated on the surface of the first anti-glare hardened coating, the treatment is carried out at 80 ℃ for 2min, after the solvent is volatilized, the coating is cured by ultraviolet light, and the UV curing energy is 450mJ/cm 2 ～780mJ/cm 2 The light curing process involves curing the second anti-glare hardened coating and composite cross-linking curing of the UV-curable resin in the first anti-glare hardened coating to establish a tight connection between the first and second anti-glare hardened coatings.
The anti-fog and anti-glare hardened film is a direct contact interface of a user, so that the first anti-glare hardened coating is arranged on the surface of the transparent support, on one hand, the thickness of the coating reaches the standard and meets certain hardness and wear-resistant requirements, and on the other hand, the first organic particles in the first anti-glare hardened coating provide a step effect for the second organic particles. In order to satisfy high gloss, low roughness, and anti-glare and high definition, the coating thickness and particle size need to satisfy the following relationship: D1-L1 is more than 0 and less than L2, and D2+ D1-L1 is more than L2.
The thermosetting resin in the first anti-glare hardened coating layer in the present invention may be polyurethane, acrylate, etc., and preferably polyurethane having a molecular weight of 1000 to 6000, such as PANDEX P-910, OD-X-2195, etc., available from DIC corporation. The UV-curable resin in the first coating and the second coating is polyurethane, acrylate, epoxy resin, etc., preferably 6-9 functionality polyurethane acrylate, such as Sadoma CN997, cyanote EB 2220, EB 5129, changxing 6145-100.
In the present invention, the first organic particles have a particle size of 5 to 12 μm and may be BM30X-5 (monodisperse BMA5 μm), MBX-8 (monodisperse PMMA8 μm), MBX-12 (monodisperse PMMA12 μm), SSX-110 (monodisperse MMA10 μm), available from water-collecting chemical Co., ltd., BRS-7HC (monodisperse PBMA 7 μm); the second organic particles have a particle size of 2 to 8 μm and may be MX-180TA (monodisperse PMAA2 μm), MX-500F (monodisperse PMAA 5.6 μm), BXS-500 (monodisperse PBMA5 μm), SEKOKAI SSX-105 (monodisperse MMA5 μm), SSX-108 (monodisperse MMA8 μm), and MB30X-8 (monodisperse PMMA8 μm). The first organic particles and the second organic particles are monodisperse particles.
The photoinitiator in the invention is one of free radical polymerization photoinitiators and cationic polymerization photoinitiators, such as benzoin and derivatives, alkyl iodonium salts and the like, and can be selected from Pasteur Irgacure TPO, lancolo 5020, IGM Omnirad 819.
The thermal curing agent in the first coating layer of the present invention is selected from isocyanate-based curing agents, such as Basonathi100ap and Basonat HB175 from Basff, or Desmodur Z4470 MPA/X from Corsai.
The leveling agent in the first coating is an acrylic leveling agent, and can be selected from Guangdong Jiaming CM-703, CM-6358N and Bick chemical BYK-358N, BYK-371. The leveling agent in the second coating is siloxane leveling agent, and can be selected from Guangdong Jiaming CM-306, basff
SL 3239。/>
In the invention, organic solvents are added to both coating liquids, and single solvents or mixed solvents of alcohols (such as ethanol, propanol and the like), esters (such as butyl acetate, ethyl acetate and the like) and ketones (such as butanone and acetone) can be selected.
The wetting dispersant in the second anti-glare hardened coating of the invention can be polyurethane dispersant, such as BYK DISPERBYK-170tf, DISPERBYK-174; or an acrylic dispersant such as DISPERBYK-2026, DISPERBYK-2025, bick chemical.
The transparent support is one of a triacetate fiber film (TAC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA) or Polyimide (PI), and the thickness of the transparent support is 40-125 mu m.
The present invention will be further described with reference to the following examples.
Example 1
The first coating layer coating liquid comprises the following components in parts by mass:
PANDEX P-910：30g
CN 997：1.5g
IPDA：0.9g
Irgacure TPO：0.08g
MBX-12：2.9g
guangdong Jiaming CM-703:1.0g
Mixing solvent: 63.62g
30g of polyurethane (PANDEX P-910, DIC corporation), 1.5g of urethane acrylate (CN 997), 0.9g of isophoronediamine (Pasteur IPDA), 0.08g of photoinitiator (Pasteur Irgacure TPO), 2.9g of first organic particles (MBX-12, monodisperse PMMA12 μm, waters chemical Co., ltd.), 1.0g of acrylic leveling agent (Guangdong Jiaming CM-703) and 63.62g of ethyl acetate/butanone 1:1 mixed solvent were poured into a beaker, and the mixture was stirred at a low speed of 300rpm for 10min and at a high speed of 1000rpm for 60min, and stirred uniformly to obtain a first coating solution.
The second coating layer coating liquid comprises the following components in parts by mass:
sartomer CN 997:35g of
Basf Irgacure TPO:1.5g
Guangdong Jiaming CM-306:0.8g
DISPERBYK-170TF：0.5g
BXS-500：0.7g
Zinc oxide nanoparticles: 0.35g
Ethyl acetate: 61.15g
35g of urethane acrylate (sartomer CN 997), 1.5g of photoinitiator (Basff Irgacure TPO), 0.8g of siloxane leveling agent (Guangdong Jiaming CM-306), 0.5g of wetting dispersant (DISPERBYK-170 TF), 1.4g of second organic particles (general grinding chemical BXS-500, monodisperse PBMA5 mu m), 0.35g of zinc oxide nanoparticles and 61.15g of mixed solvent of ethyl acetate/butanone 1:1 are poured into a beaker, stirred at a low speed of 300rpm for 10min and then at a high speed of 1000rpm for 60min, and stirred uniformly to obtain a second coating liquid.
The preparation steps of the zinc oxide nanoparticles are as follows: 1) Adding 40mL of cyclohexane and 1.5mL of emulsifier polyglycerol ricinoleate into a flask, and magnetically stirring and dispersing to obtain a cyclohexane oil phase; adding 2mL of ionized water and azo isobutyl cyano formamide into a beaker, uniformly mixing, adding a small amount of NaOH, and adjusting the pH value to 6-8 to obtain a water phase. Slowly adding the water phase into a flask filled with the oil phase, and performing ultrasonic treatment and emulsification for 30min at room temperature to obtain uniform and stable cyclohexane-water-in-oil emulsion. 2) Adding 7.8g of ZnCl 2 Pouring into a three-neck flask, and adding SOCl 2 ZnCl treated by reflux drying 2 The residual SOCl in the flask was then removed in vacuo 2 20.7g of CH 3 n-Bu of MgI 2 Slowly dripping the O solution into a flask, stirring vigorously, cooling and refluxing for 50 hours at 70 ℃, distilling at the temperature of 130-160 ℃ to obtain dimethyl zinc, dissolving the obtained dimethyl zinc in a toluene solvent, dripping 3.5g of ethanol, stirring the solution at room temperature for 12 hours, drying in vacuum to remove toluene to obtain a white solid, and washing and drying with cyclohexane to obtain an isopropanol methyl zinc precursor. 3) Dissolving an isopropanol methyl zinc precursor in cyclohexane, fully dispersing, slowly dropwise adding into an emulsion, and when the concentration of the precursor in a cyclohexane oil phase reaches saturation, diffusing the precursor to an oil-water interface to form zinc oxide nanoparticles, so as to obtain a triangular prism crystal structure under the action of different coordinated oxygen of ether groups and alcohol groups. And dispersing a water layer and an oil layer by centrifugation, and filtering the water layer to obtain the zinc oxide nano-particles.
And coating the first coating liquid on one surface of a 60-micrometer cellulose Triacetate (TAC) film, placing the film in an oven at 80 ℃ for 3min, and then placing the film in an oven at 100 ℃ for curing for 2min to obtain a first coating. Coating the second coating liquid on the surface of the first coating layer, placing the first coating layer in an oven at 80 ℃ for 3min, and curing with UV (ultraviolet) at the energy of 450mJ/cm 2 ～780mJ/cm 2 A second coating layer was obtained, and an antifogging antiglare, hard-set film was obtained, in which L1=7 μm and L2=8 μm.
Example 2
The first coating layer coating liquid comprises the following components in parts by mass:
OD-X-2195：40g
cyanogen EB 2220:3.0g
Thermal curing agent: 3.5g
Lencolo 5020：0.3g
SSX-110：6.2g
ByK-358N:1.5g
Mixing solvent: 45.5g
40g of polyurethane (OD-X-2195, DIC Co., ltd.), 3.0g of urethane acrylate (Cycote EB 2220), 0.9g of isophoronediamine (Pasteur IPDA), 0.3g of photoinitiator (Lencolo 5020), 6.2g of first organic particles (SSX-110, monodisperse MMA10 μm), 1.0g of leveling agent of acrylic acid (ByK-358N, bikk chemical) and 45.5g of a mixed solvent of ethyl acetate/butanone 8978 zft 8978 were poured into a beaker, and stirred at a low speed of 300rpm for 10min and at a high speed of 1000rpm for 60min to obtain a first coating solution.
The second coating layer coating liquid comprises the following components in parts by mass:
cyanogen EB 2220:40g of
Lencolo 5020：4.5g
Basf Efka SL 3239:1.5g
DISPERBYK-170TF：1.3g
Hydroprocess chemical corporation SSX-108:3.25g
Zinc oxide nanoparticles: 1.2
Mixing solvent: 48.25g
40g of urethane acrylate (cyanotex EB 2220), 4.5g of photoinitiator (Lencolo 5020), 1.5g of siloxane leveling agent (basf Efka SL 3239), 1.3g of wetting dispersant (DISPERBYK-170 TF), 3.25g of second organic particles (SSX-108, hydroscopical chemical Co., ltd., monodisperse MMA8 μm), 1.2g of zinc oxide nanoparticles and 48.25g of a mixed solvent of ethyl acetate/butanone 8978 zft 8978 are poured into a beaker, and stirred at a low speed of 300rpm for 10min and at a high speed of 1000rpm for 60min, and stirred uniformly to obtain a second coating solution.
The zinc oxide nanoparticles preparation procedure was as described in example 1. Coating and curing were as described in example 1, with a coating thickness L1=6 μm and L2=9 μm.
Example 3
The first coating layer coating liquid consists of the following components in parts by mass:
thermosetting resin: 45g of
Yangxing 6145-100:3.5g
Thermal curing agent: 4.0g
IGM Omnirad 819：0.3g
MBX-8：5.8g
ByK-371:2.5g
Mixing solvent: 38.9g
45g of polyurethane (PANDEX P-910, DIC corporation), 3.5g of urethane acrylate (Changxing 6145-100), 4.0g of isophorone diamine (Pasteur IPDA), 0.3g of photoinitiator (IGM Omnirad 819), 7.2g of first organic particles (MBX-8, monodisperse PMMA8 μm), 2.5g of acrylic leveling agent (BYK-371, bikk chemical) and 38.9g of mixed solvent of ethyl acetate/butanone 1:1 are poured into a beaker, stirred at a low speed of 300rpm for 10min and then at a high speed of 1000rpm for 60min, and stirred uniformly to obtain a first coating solution.
The second coating layer coating liquid comprises the following components in parts by mass:
yangxing 6145-100:55g
IGM Omnirad 819：6g
Guangdong Jiaming CM-306:1.8g
DISPERBYK-2025：1.7g
Chemical MX-180TA:1.35g
Zinc oxide nanoparticles: 0.8g
Mixing solvent: 33.35g
55g of urethane acrylate (Changxing 6145-100), 6g of photoinitiator (IGM Omnirad 819), 1.8g of siloxane leveling agent (Guangdong Jiaming CM-306), 1.7g of wetting dispersant (DISPERBYK-2025), 1.35g of second organic particles (Miyao chemical MX-180TA, monodisperse PMAA2 mu m), 0.8g of zinc oxide nanoparticles and a mixed solvent of 33.35 ethyl acetate/butanone 1:1 are poured into a beaker, stirred at a low speed of 300rpm for 10min, then at a high speed of 1000rpm for 60min and stirred uniformly to obtain a second coating liquid.
The zinc oxide nanoparticles preparation procedure was as described in example 1. Coating and curing as described in example 1, coating thickness L1=5 μm, L2=4 μm.
Example 4
The first coating layer coating liquid comprises the following components in parts by mass:
thermosetting resin: 35g of
Cyanogen special EB 5129:2.5g
Thermal curing agent: 2.8g
Lanketway Lencolo 5020:0.175g
MBX-8 (monodisperse PMMA8 μm): 4.48g
ByK-371:2.05g
Mixing solvent: 52.995g
35g of polyurethane (PANDEX P-910, DIC corporation), 2.5g of urethane acrylate (Cyanote EB 5129), 2.8g of isophoronediamine (Pasteur IPDA), 0.175g of photoinitiator (Lencolo 5020, blue Clay), 4.0g of first organic particles (MBX-8, monodisperse PMMA8 μm, waters chemical Co., ltd.), 2.05g of an acrylic leveling agent (BYK-371, bikk chemical) and 8978 zft 8978 g of a mixed solvent were poured into a beaker, and the mixture was stirred at a low speed of 300rpm for 10min and at a high speed of 1000rpm for 60min to obtain a first coating solution.
The second coating layer coating liquid comprises the following components in parts by mass:
cyanogen EB 5129:50g
Lanketway Lencolo 5020:5.0g
Basf Efka SL 3239:1.7g
DISPERBYK-2025：1.65g
Hydroprocess chemical corporation SSX-105:1.225g
Zinc oxide nanoparticles: 1.2g
Mixing solvent: 39.225g
50g of urethane acrylate (Cyanote EB 5129), 5.0g of photoinitiator (Lencolo 5020 in Lancocurel), 1.7g of a siloxane leveling agent (Pasteur Efka SL 3239), 1.65g of a wetting dispersant (DISPERBYK-2025), 1.225g of second organic particles (SSX-105, mono-dispersed MMA5 μm), 1.2g of zinc oxide nanoparticles and 39.255g of a mixed solvent are poured into a beaker, stirred at a low speed of 300rpm for 10min and then at a high speed of 1000rpm for 60min, and stirred uniformly to obtain a second coating liquid.
The zinc oxide nanoparticles preparation procedure was as described in example 1. Coating and curing as described in example 1, coating thickness L1=5 μm, L2=6 μm.
Comparative example 1
The first coating layer coating liquid comprises the following components in parts by mass:
PANDEX P-910：30g
CN 997：1.5g
IPDA：0.9g
Irgacure TPO：0.08g
BXS-500：2.9g
guangdong Jiaming CM-703:1.0g
Mixing solvent: 63.62g
30g of polyurethane (PANDEX P-910, DIC corporation), 1.5g of urethane acrylate (CN 997), 0.9g of isophorone diamine (Pasteur IPDA), 0.08g of photoinitiator (Pasteur Irgacure TPO), 2.9g of first organic particles (Soken chemical BXS-500, monodisperse PBMA5 μm), 1.0g of acrylic leveling agent (Guangdong Jiaming CM-703) and 63.62g of ethyl acetate/butanone 1:1 mixed solvent are poured into a beaker, and the mixture is stirred at a low speed of 300rpm for 10min and then at a high speed of 1000rpm for 60min, and stirred uniformly to obtain a first coating liquid.
The second coating layer coating liquid comprises the following components in parts by mass:
sartomer CN 997:35g of
Basf Irgacure TPO:1.5g
Guangdong Jiaming CM-306:0.8g
DISPERBYK-170TF：0.5g
BXS-500：0.7g
Zinc oxide nanoparticles: 0.35g
Ethyl acetate: 61.15g
35g of urethane acrylate (sartomer CN 997), 1.5g of photoinitiator (Basff Irgacure TPO), 0.8g of siloxane leveling agent (Guangdong Jiaming CM-306), 0.5g of wetting dispersant (DISPERBYK-170 TF), 1.4g of second organic particles (general grinding chemical BXS-500, monodisperse PBMA5 mu m), 0.35g of zinc oxide nanoparticles and 61.15g of mixed solvent of ethyl acetate/butanone 1:1 are poured into a beaker, stirred at a low speed of 300rpm for 10min and then at a high speed of 1000rpm for 60min, and stirred uniformly to obtain a second coating liquid.
The zinc oxide nanoparticles preparation procedure was as described in example 1. Coating and curing methods as described in example 1, an antifogging and antiglare hardened film was obtained, with coating thicknesses L1=7 μm and L2=8 μm.
Comparative example 2
The first coating layer coating liquid consists of the following components in parts by mass:
OD-X-2195：40g
cyanogen EB 2220:3.0g
Thermal curing agent: 3.5g
Lencolo 5020：0.3g
SSX-110：6.2g
Byk chemistry BYK-358N:1.5g
Mixing solvent: 45.5g
40g of polyurethane (OD-X-2195, DIC Co., ltd.), 3.0g of urethane acrylate (Cycote EB 2220), 0.9g of isophoronediamine (Pasteur IPDA), 0.3g of photoinitiator (Lencolo 5020), 6.2g of first organic particles (SSX-110, monodisperse MMA10 μm), 1.0g of leveling agent of acrylic acid (ByK-358N, bikk chemical) and 45.5g of a mixed solvent of ethyl acetate/butanone 8978 zft 8978 were poured into a beaker, and stirred at a low speed of 300rpm for 10min and at a high speed of 1000rpm for 60min to obtain a first coating solution.
The second coating layer coating liquid comprises the following components in parts by mass:
cyanogen EB 2220:40g of
Lencolo 5020：4.5g
Basf Efka SL 3239:1.5g
DISPERBYK-170TF：1.3g
Hydroprocess chemical corporation SSX-108:3.25g
Commercially available zinc oxide nanoparticles: 1.2g
Mixing solvent: 48.25g
40g of urethane acrylate (cyanote EB 2220), 4.5g of photoinitiator (Lencolo 5020), 1.5g of siloxane leveling agent (basf Efka SL 3239), 1.3g of wetting dispersant (DISPERBYK-170 TF), 3.25g of second organic particles (SSX-108, monodisperse MMA8 μm), 1.2g of commercially available zinc oxide nanoparticles (Allandin reagent, 99%, particle size is less than or equal to 100 nm), and 48.25g of ethyl acetate/butanone 1:1 mixed solvent are poured into a beaker, and the mixture is stirred at low speed of 300rpm for 10min, then at high speed of 1000rpm for 60min, and stirred uniformly to obtain a second coating liquid.
The zinc oxide nanoparticles preparation procedure was as described in example 1. Coating and curing were as described in example 1, with a coating thickness L1=6 μm and L2=9 μm.
The hardened films prepared in the above examples and comparative examples were subjected to performance tests, and the test results are shown in table 1.
TABLE 1 hardened film Performance test results
(1) Light transmittance
The haze transmittance was measured using a haze meter (Nippon Denshoku Co., ltd.; model No. NDH 2000N).
(2) Roughness of
The appearance and roughness of the coupons were tested using a 3D laser microscope (Keyence, model VK-X3050).
(3) Degree of gloss
The 60 ℃ gloss of the test piece was measured using a gloss meter (Sanchen 3ns, model: NHG 60M).
(4) Antifogging property
And (3) carrying out antifogging test on the experimental sample by referring to a rapid hot fog method in three standard test methods in the standard GB/T1.1-2009, wherein the antifogging grade is 1: the visual chart is completely transparent and has no water drops, and the definition degree of the visual chart is completely consistent with that before the test; 2: the clearness is good, and a small amount of uneven large water drops exist; the definition of the visual chart with the area of more than 50 percent is completely consistent with that before the test; 3: the visual chart is basically transparent, more water drops exist, and the primary and secondary visual charts deform; 4: semitransparent, and a small amount of water drops are found below 0.1 of an eye chart; 5: completely opaque, completely obscured visual chart.
As can be seen from the data of examples 1 to 4 in table 1, (1) by controlling the thickness of the coating and the matching of the first organic particles in the first layer and the second organic particles in the second layer, the cured film of the present invention can achieve effective curing protection while achieving good control of haze on one hand, such as example 3, the particle size of the second organic particles is as small as 2 μm, but by the thickness of the first organic particles in the first layer and the two coating layers, a higher haze (20.08%) can also be achieved; on the other hand, through the step effect of the first organic particles in the first layer and the control of the coating thickness, under higher haze, the glossiness (60 ℃) can be as high as 120, and the roughness can be as low as less than 1 μm, so that the problems of low glossiness and high roughness of the high-haze protective film are effectively solved. (2) By adding the self-made triangular prism-shaped nano zinc oxide particles into the second coating, on one hand, the antifogging effect is effectively achieved, and the antifogging effect can reach more than level 2 through testing the antifogging property by a rapid hot fog method; on the other hand, the light transmittance and the ultraviolet blocking effect are effectively improved, in the embodiment, the light transmittance is over 91 percent, and the ultraviolet blocking rate of 380nm wavelength can reach 81.3 percent at most.
By comparing example 1 with comparative example 1, the particle diameters of the first organic particles and the second organic particles of comparative example 1 do not meet the relationship of 0 < D1-L1 < L2, and D2+ D1-L1 > L2, both haze and gloss are significantly reduced, roughness is significantly improved, and antifogging property is also reduced.
By comparing example 2 with comparative example 2, the zinc oxide nanoparticles used in comparative example 2 were commercial zinc oxide as an alatin reagent, and the antifogging property was measured by a rapid hot fogging method, and the antifogging effect was judged to be grade 4, and by comparing example 2, the conventional zinc oxide had almost no antifogging effect, and thus the advantage of the triangular nano zinc oxide antifogging property was seen.
Claims (10)
1. An antifogging and antiglare hardened film characterized in that: the hard coating film consists of a transparent support and two layers of anti-dazzle hard coating layers coated on one surface of the transparent support;
the first anti-glare hardened coating is obtained by coating and curing a coating liquid prepared from the following components in parts by mass: heat-curable resin: 30 to 45 percent;
UV curing resin: 1.5 to 3.5;
photoinitiator (2): 0.08 to 0.3;
thermal curing agent: 0.9 to 4.0;
first organic particles: 2.9 to 6.2;
leveling agent: 1.0 to 2.5;
solvent: 38.9 to 63.62;
the second anti-dazzle hardening coating is formed by coating and curing a coating liquid prepared from the following components in parts by mass: UV curing resin: 35 to 55 percent;
photoinitiator (2): 1.5 to 6;
leveling agent: 0.8 to 1.8;
wetting and dispersing agent: 0.5 to 1.7;
second organic particles: 0.7 to 3.25;
zinc oxide nanoparticles: 0.35 to 1.2;
solvent: 33.35 to 61.15.
2. The antifogging antiglare hardened film of claim 1, characterized in that: the particle size of the first organic particles is D1= 5-12 μm, the particle size of the second organic particles is D2= 2-8 μm, and the first organic particles and the second organic particles are all monodisperse organic particles; the first anti-glare hardened coating has a thickness L1, the second anti-glare hardened coating has a thickness L2, and L1, L2, D1 and D2 satisfy the following relations: D1-L1 is more than 0 and less than L2, and D2+ D1-L1 is more than L2.
3. The antifogging antiglare, hard-coated film of claim 1, wherein: the zinc oxide nano particles are triangular prism-shaped, and the particle size is 50-120 nm.
4. The antifogging antiglare hardened film of claim 3, characterized in that: the zinc oxide nano particles are prepared by a microemulsion method and comprise the following preparation steps:
a. preparation of a cyclohexane-water-in-oil emulsion: adding 40mL of cyclohexane and 1.5mL of emulsifier polyglycerol ricinoleate into a flask, and magnetically stirring and dispersing to obtain a cyclohexane oil phase; adding 2mL of deionized water and azo isobutyl cyano formamide into a beaker, uniformly mixing, adding a small amount of NaOH, and adjusting the pH to 6-8 to obtain a water phase; slowly adding the water phase into a flask filled with the oil phase, and rapidly stirring and emulsifying at room temperature for 30min to obtain uniform and stable cyclohexane-water-in-oil emulsion; head group ether group and alcohol group in emulsifier polyglycerol ricinoleate are concentrated at an oil-water interface;
b. preparation of isopropanol methyl zinc precursor: 7.8g of ZnCl 2 Pouring into a three-neck flask, and adding SOCl 2 ZnCl treated by reflux drying 2 The residual SOCl in the flask was then removed in vacuo 2 20.7g of CH 3 n-Bu of MgI 2 Slowly dripping the O solution into a flask, stirring violently, cooling and refluxing for 50 hours at 70 ℃, distilling at 130-160 ℃ to obtain dimethyl zinc, dissolving the obtained dimethyl zinc in a toluene solvent, dripping 3.5g of ethanol, stirring the solution at room temperature for 12 hours, drying in vacuum to remove toluene to obtain a white solid, and washing and drying with cyclohexane to obtain an isopropanol methyl zinc precursor;
c. formation of zinc oxide nanoparticles: dissolving an isopropanol methyl zinc precursor in a cyclohexane solvent, fully dispersing, slowly dropwise adding the isopropanol methyl zinc precursor into a cyclohexane-water-in-oil emulsion, when the concentration of the isopropanol methyl zinc precursor in a cyclohexane oil phase reaches saturation, diffusing the isopropanol methyl zinc precursor to an oil-water interface to form zinc oxide nano particles, and obtaining a triangular prism crystal structure under the action of different coordinated oxygen of ether groups and alcohol groups;
d. centrifugally dispersing the water layer and the oil layer, and filtering the water layer to obtain the zinc oxide nano-particles.
5. The antifogging antiglare hardened film of claim 1, characterized in that: the first organic particles are one of butyl methacrylate, polymethyl methacrylate, methyl methacrylate or polybutyl methacrylate; the second organic particles are one of polymethacrylic acid, polybutylmethacrylate, methylmethacrylate or polymethylmethacrylate.
6. The antifogging antiglare, hard-coated film of claim 1, wherein: the thermosetting resin used in the first anti-glare hardened coating is polyurethane, and the molecular weight of the thermosetting resin is 1000-6000; the UV curing resin is polyurethane acrylate, and the functionality of the UV curing resin is 6-9; the quality of the UV curing resin is not higher than 8% of that of the thermosetting resin, and the first anti-dazzle hardening coating is subjected to thermosetting at 100-120 ℃ for 2-5 min, so that the thermosetting resin is completely cured.
7. The antifogging antiglare hardened film of claim 1, characterized in that: the UV curing resin in the second anti-dazzle hardening coating is polyurethane acrylate with 6-9 functionality.
8. The antifogging antiglare hardened film of claim 1, characterized in that: the leveling agent in the first anti-dazzle hardening coating is an acrylic leveling agent; and the flatting agent in the second anti-dazzle hardening coating is an organic silicon flatting agent.
9. The antifogging antiglare hardened film of claim 1, characterized in that: the transparent support is one of a triacetate fiber film (TAC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA) or Polyimide (PI), and the thickness of the transparent support is 40-125 mu m.
10. The antifogging antiglare hardened film of claim 1, characterized in that: the first anti-glare hardened coating and the second anti-glare hardened coating are coated in one of a rolling coating mode, a blade coating mode, a bar coating mode and a gravure coating mode.
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| CN202211498137.5A Active CN115850803B (en) | 2022-11-27 | 2022-11-27 | Antifog anti-dazzle hardening film |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014084008A1 (en) * | 2012-11-27 | 2014-06-05 | 東レフィルム加工株式会社 | Hard coat film and transparent conducting film |
| CN107474336A (en) * | 2017-07-03 | 2017-12-15 | 三六度(中国)有限公司 | A kind of lightweight rubber composition and its application |
| CN107840982A (en) * | 2017-11-09 | 2018-03-27 | 合肥乐凯科技产业有限公司 | A kind of anti-dazzle optical hardening film of fine definition |
| CN111045119A (en) * | 2019-12-19 | 2020-04-21 | 合肥乐凯科技产业有限公司 | Surface treatment film and polaroid thereof |
| CN114213961A (en) * | 2021-12-21 | 2022-03-22 | 合肥乐凯科技产业有限公司 | Ultraviolet-proof hardening film |
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| WO2014084008A1 (en) * | 2012-11-27 | 2014-06-05 | 東レフィルム加工株式会社 | Hard coat film and transparent conducting film |
| CN107474336A (en) * | 2017-07-03 | 2017-12-15 | 三六度(中国)有限公司 | A kind of lightweight rubber composition and its application |
| CN107840982A (en) * | 2017-11-09 | 2018-03-27 | 合肥乐凯科技产业有限公司 | A kind of anti-dazzle optical hardening film of fine definition |
| CN111045119A (en) * | 2019-12-19 | 2020-04-21 | 合肥乐凯科技产业有限公司 | Surface treatment film and polaroid thereof |
| CN114213961A (en) * | 2021-12-21 | 2022-03-22 | 合肥乐凯科技产业有限公司 | Ultraviolet-proof hardening film |
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