CN115850803A - An anti-fog and anti-glare hardened film - Google Patents

Abstract

An anti-fog and anti-glare hardened film, which is composed of a transparent support and two layers of anti-glare hardened coatings coated on one side of the transparent support; the first anti-glare hardened coating is made of the following components in parts by mass The coating solution is coated and cured to obtain: thermal curing resin: 30-45; UV curing resin: 1.5-3.5; photoinitiator: 0.08-0.3; thermal curing agent: 0.9-4.0; first organic particle: 2.9-6.2; Leveling agent: 1.0-2.5; solvent: 38.9-63.62; the second anti-glare hard coating is formed by coating and curing the coating solution made of the following components by mass: UV curable resin: 35-55; photoinitiator : 1.5～6; Leveling agent: 0.8～1.8; Wetting and dispersing agent: 0.5～1.7; Second organic particle: 0.7～3.25; Zinc oxide nanoparticle: 0.35～1.2; Solvent: 33.35～61.15. The cured film of the invention has the technical characteristics of excellent anti-fog property, high definition, high gloss and low roughness, and also has a certain ultraviolet blocking effect.

Description

Anti-fog and anti-glare hardened film

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 Art

The anti-glare hardened film can provide basic protection for display devices, and can also use the concave-convex microstructure on its surface to diffusely reflect incident strong light, thereby achieving an anti-glare effect and improving image viewing effects.

At present, anti-glare protective films for displays are usually made by adding organic or inorganic particles to resin-based coatings to form an uneven microstructure on the surface of the coating, so as to achieve a diffuse reflection effect on the incident light and realize the anti-glare function. In actual production and application, on the one hand, it is necessary to perform coating and lamination treatments on the basis of the hardened film before proceeding to the next process. However, the use of particles to produce surface unevenness will cause a decrease in surface gloss, and the increase in roughness increases the difficulty of coating and lamination; on the other hand, display devices, especially for outdoor equipment, need to adapt to weather factors and need to maintain usability in extreme weather, that is, they need a certain degree of anti-fog properties.

Summary of the invention

In order to overcome the drawbacks of the prior art, the present invention provides an anti-fog and anti-glare hardened film, which is coated with two layers of anti-glare coating on a support, organic particles are added to the coating, and the particle size and coating thickness of the organic particles are controlled, and triangular prism-shaped zinc oxide nanoparticles are added to the second coating, so that it has the advantages of high clarity, high gloss and low roughness.

The technical solution adopted by the present invention to solve the technical problem is:

An anti-fog and anti-glare hardened film, the hardened film is composed of a transparent support and two layers of anti-glare hardened coatings coated on one side of the transparent support;

The first anti-glare hardened coating is obtained by coating and curing a coating solution made of the following components in parts by mass: 30 to 45 parts of a thermosetting resin;

UV curing resin: 1.5~3.5;

Photoinitiator: 0.08～0.3;

Thermal curing agent: 0.9～4.0;

First organic particles: 2.9-6.2;

Leveling agent: 1.0～2.5;

Solvent: 38.9～63.62;

The second anti-glare hardened coating is formed by coating and curing a coating solution made of the following components in parts by mass: UV curable resin: 35-55;

Photoinitiator: 1.5～6;

Leveling agent: 0.8～1.8;

Wetting and dispersing agent: 0.5～1.7;

Second organic particles: 0.7-3.25;

Zinc oxide nanoparticles: 0.35-1.2;

Solvent: 33.35～61.15.

The above-mentioned anti-fog and anti-glare hardened film, the first organic particle size is D1 = 5~12μm, the second organic particle size is D2 = 2~8μm, and both are monodisperse organic particles; the thickness of the first anti-glare hardened coating is L1, the thickness of the second anti-glare hardened coating is L2, and L1, L2, D1, D2 satisfy the following relationship: 0＜D1-L1＜L2, D2+D1-L1＞L2.

In the anti-fog and anti-glare hardened film, the zinc oxide nanoparticles are in the shape of triangular prisms and have a particle size of 50 to 120 nm.

The anti-fog and anti-glare hardened film, the zinc oxide nanoparticles are prepared by a microemulsion method, and the preparation steps are as follows:

a. Preparation of cyclohexane-water oil-in-water emulsion: 40 mL of cyclohexane and 1.5 mL of emulsifier polyglycerol ricinoleate were added to a flask, and the cyclohexane oil phase was dispersed by magnetic stirring; 2 mL of deionized water and azoisobutylcyanamide were added to a beaker, and a small amount of NaOH was added after mixing evenly, and the pH was adjusted to 6-8 to obtain an aqueous phase; the aqueous phase was slowly added to the flask containing the oil phase, and the emulsification was rapidly stirred for 30 minutes at room temperature to obtain a uniform and stable cyclohexane-water oil-in-water emulsion; the head groups (ether groups, alcohol groups) in the emulsifier polyglycerol ricinoleate were concentrated at the oil-water interface;

b. Preparation of methyl zinc isopropoxide precursor: 7.8 g _ZnCl2 was poured into a three-necked flask, and _ZnCl2 was treated with _SOCl2 by reflux drying, and then the residual _SOCl2 in the flask was removed in vacuum, and 20.7 g _CH3MgI n- _Bu2O solution was slowly added dropwise into the flask while stirring vigorously, and after cooling and refluxing at 70°C for 50 hours, dimethyl zinc was obtained by distillation in the temperature range of 130-160°C, and the obtained dimethyl zinc was dissolved in toluene solvent, and 3.5 g ethanol was added dropwise, and the solution was stirred at room temperature for 12 hours, and toluene was removed by vacuum drying to obtain a white solid, which was then washed and dried with cyclohexane to obtain a methyl zinc isopropoxide precursor;

c. Formation of zinc oxide nanoparticles: dissolve the isopropanol methyl zinc precursor in an ethanol solvent, and after fully dissolving, slowly add it dropwise to a cyclohexane-water oil-in-water emulsion. When the concentration of the isopropanol methyl zinc precursor in the cyclohexane oil phase reaches saturation, the isopropanol methyl zinc precursor will diffuse to the oil-water interface to form zinc oxide nanoparticles, and a triangular prism crystal structure is obtained under the action of different coordinated oxygens of the ether group and the alcohol group;

d. Centrifugally disperse the water layer and the oil layer, and then filter the water layer to obtain zinc oxide nanoparticles.

In the above 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, polybutyl methacrylate, methyl methacrylate or polymethyl methacrylate.

In the above-mentioned anti-fog and anti-glare hardened film, the thermosetting resin used in the first anti-glare hardening coating is polyurethane with a molecular weight of 1000 to 6000, and the UV curing resin is polyurethane acrylate with a functionality of 6 to 9; the mass of the UV curing resin is not higher than 8% of the mass of the thermosetting resin, and the first anti-glare hardening coating is thermally cured at 100 to 120°C for 2 to 5 minutes to completely cure the thermosetting resin.

In the above anti-fog and anti-glare hardened film, the UV curable resin in the second anti-glare hardened coating layer is polyurethane acrylate with a functionality of 6 to 9.

In the above-mentioned anti-fog and anti-glare hardened film, the leveling agent in the first anti-glare hardened coating layer is an acrylic leveling agent; and the leveling agent in the second anti-glare hardened coating layer is a silicone leveling agent.

The above-mentioned anti-fog and anti-glare hardened film, the transparent support is one of triacetate cellulose film (TAC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA) or polyimide (PI), and its thickness is 40 to 125 μm.

In the above-mentioned anti-fog and anti-glare hardened film, the coating method of the first anti-glare hardened coating layer and the second anti-glare hardened coating layer is one of roller coating, blade coating, rod coating, or gravure coating.

The beneficial effects of the present invention are:

1. The anti-fog and anti-glare hardened film of the present invention consists of a transparent support and two layers of anti-glare coatings. The coating thickness and particle size are controlled to meet the following conditions: 0＜D1-L1＜L2, D2+D1-L1＞L2, so that the first organic particles provide a "step" for the second organic particles in the second coating. On the one hand, it is beneficial to uniformly arrange the second organic particles, reduce surface roughness, and improve glossiness; on the other hand, under the same haze requirement, the required particle size is smaller, thereby improving the clarity of the anti-glare hardened film and enhancing the picture quality.

2. The surface of the anti-fog and anti-glare hardened film of the present invention is distributed with protruding organic particles and nano zinc oxide particles, wherein the zinc oxide particles are in the shape of a triangular prism, which form dense sharp corners on the surface of the coating, forming a super hydrophilic surface, so that water cannot form water droplets on its surface, thereby effectively achieving an anti-fog effect. In addition, due to the excellent optical properties of zinc oxide, the light transmittance and UV resistance of the coating are also effectively improved.

3. The anti-fog and anti-glare hardened film of the present invention is a user direct contact interface and requires good wear resistance and hardness. The present invention uses a second organic particle with a smaller particle size to improve the surface while ensuring the coating thickness by establishing a double coating, thereby ensuring the wear resistance and hardness performance of the coating.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of the structure of the anti-fog and anti-glare hardened film of the present invention.

In the figure: 1. zinc oxide nanoparticles; 2. second organic particles; 3. second anti-glare hardening coating; 4. first organic particles; 5. first anti-glare hardening coating; 6. transparent support.

DETAILED DESCRIPTION

In order to solve the existing problems of anti-glare hardened films, the anti-fog and anti-glare hardened film of the present invention uses two anti-glare layers, and an improved anti-fog and anti-glare hardened film is obtained by controlling the coating thickness and the particle size of organic anti-glare particles in the coating.

Referring to FIG. 1 , the second anti-glare hardening coating of the present invention is coated on the surface of the first anti-glare hardening coating, and the thickness of the first anti-glare hardening coating and the particle size of the first organic particles are controlled to satisfy D1>L1. The portion of the first organic particles in the first anti-glare hardening coating that exceeds the coating thickness can provide a certain height for the second anti-glare hardening coating, acting 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 hardening coating, thereby controlling the protrusion height of the second organic particles, and achieving a high gloss and low roughness technical effect. The resin in the first anti-glare hardening coating can increase the total coating thickness, ensure the hardness of the hardened film, etc., and the UV curing resin therein performs a photocuring effect together with the UV curing resin in the second anti-glare hardening coating to enhance the tightness of the first and second anti-glare hardening coatings.

In the present invention, the zinc oxide nanoparticles added to the second anti-glare hardening coating are distributed on the surface of the coating to form dense sharp corners in the coating, forming a super-hydrophilic surface, increasing the surface tension of water, thereby effectively achieving an anti-fog effect. The zinc oxide nanoparticle preparation method is as follows:

a. Preparation of water-in-oil emulsion (cyclohexane-water): Add 40 mL of cyclohexane and 1.5 mL of emulsifier polyglycerol ricinoleate to a flask, and disperse by magnetic stirring to obtain a cyclohexane oil phase; in a beaker, add 2 mL of ionized water and azoisobutylcyanamide, mix well, add a small amount of NaOH, adjust the pH to 6-8, and obtain an aqueous phase. Slowly add the aqueous phase to the flask containing the oil phase, and emulsify by ultrasonic treatment at room temperature for 30 minutes to obtain a uniform and stable cyclohexane-water 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 methyl zinc isopropoxide precursor: 7.8 g _ZnCl2 was poured into a three-necked flask, and _ZnCl2 was treated with _SOCl2 by reflux drying. The residual _SOCl2 in the flask was removed in vacuum, and 20.7 g _CH3MgI n- _Bu2O solution was slowly added dropwise into the flask while stirring vigorously. After cooling and refluxing at 70°C for 50 hours, dimethyl zinc was obtained by distillation in the temperature range of 130-160°C. The obtained dimethyl zinc was dissolved in toluene solvent, and 3.5 g ethanol was added dropwise. The solution was stirred at room temperature for 12 hours, and toluene was removed by vacuum drying to obtain a white solid, which was then washed and dried with cyclohexane to obtain a methyl zinc isopropoxide precursor.

c. Formation of zinc oxide nanoparticles: Dissolve the isopropanol methyl zinc precursor in cyclohexane, fully disperse it, and slowly add it to the emulsion. When the concentration of the precursor in the cyclohexane oil phase reaches saturation, the precursor will diffuse to the oil-water interface to form zinc oxide nanoparticles, and a triangular prism crystal structure is obtained under the action of different coordinated oxygen of the ether group and the alcohol group. Disperse the water layer and the oil layer by centrifugation, and then filter the water layer to obtain zinc oxide nanoparticles.

During the formation of zinc oxide nanoparticles, the precursor diffuses from the oil phase to the water phase and reacts with water at the oil-water interface. The ether groups and alcohol groups in the structure of the emulsifier polyglycerol ricinoleate gathered at the oil-water interface act on different crystal faces due to the different types of coordinated oxygen atoms, thereby controlling the anisotropic growth of the crystals to obtain triangular prism-shaped zinc oxide nanocrystals.

In the present invention, the first anti-glare hardening coating is cured by thermal curing, the curing temperature is 100-120°C, and the time is 2-5 minutes. After the first anti-glare hardening coating is thermally cured and cooled, the second anti-glare hardening coating is coated on the surface of the first anti-glare hardening coating, and then treated at 80°C for 2 minutes. After the solvent evaporates, the coating is photocured by ultraviolet light, and the UV curing energy is 450mJ/ ^cm2-780mJ / ^cm2 . This photocuring process involves the curing of the second anti-glare hardening coating and the composite cross-linking curing of the UV light-curing resin in the first anti-glare hardening coating, and a tight connection is established between the first and second anti-glare hardening coatings.

The anti-fog and anti-glare hardened film of the present invention is the interface that users directly contact. Therefore, a first anti-glare hardened coating is set on the surface of the transparent support. On the one hand, the coating thickness meets the standard and meets certain hardness and wear resistance requirements. 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 achieve high gloss, low roughness, anti-glare and high clarity, the coating thickness and particle size need to meet the following relationship: 0＜D1-L1＜L2, D2+D1-L1＞L2.

The thermosetting resin in the first anti-glare hardening coating of the present invention can be polyurethane, acrylate, etc., preferably polyurethane with a molecular weight of 1000-6000, such as DIC Corporation PANDEX P-910, OD-X-2195, etc. The UV curing resin in the first coating and the second coating is polyurethane, acrylate, epoxy resin, etc., preferably polyurethane acrylate with a functionality of 6-9, such as Sartomer CN 997, Cytec 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 can be BM30X-5 (monodisperse BMA 5 μm), MBX-8 (monodisperse PMMA 8 μm), MBX-12 (monodisperse PMMA 12 μm), SSX-110 (monodisperse MMA 10 μm), and BRS-7HC (monodisperse PBMA 7 μm) produced by Sekisui Chemical Co., Ltd.; the second organic particles have a particle size of 2 to 8 μm, and can be MX-180TA (monodisperse PMAA 2 μm), MX-500F (monodisperse PMAA 5.6 μm), and BXS-500 (monodisperse PBMA 5 μm) produced by Soken Chemical Co., Ltd., SSX-105 (monodisperse MMA 5 μm), SSX-108 (monodisperse MMA 8 μm), and MB30X-8 (monodisperse PMMA 8 μm) produced by Sekisui Chemical Co., Ltd. Both the first organic particles and the second organic particles are monodisperse particles.

The photoinitiator in the present invention is one of a free radical polymerization photoinitiator and a cationic polymerization photoinitiator, such as benzoin and its derivatives, alkyl iodonium salts, etc., and BASF Irgacure TPO, Lencolo 5020, and IGMOmnirad 819 can be selected.

In the present invention, the heat curing agent in the first coating layer is selected as an isocyanate curing agent, and Basonat HI100ap and Basonat HB175 of BASF, or Desmodur Z4470 MPA/X of Covestro can be selected.

SL 3239。The leveling agent in the first coating of the present invention is an acrylic leveling agent, and Guangdong Jiaming CM-703, CM-6358N and BYK Chemical BYK-358N, BYK-371 can be selected. The leveling agent in the second coating is a siloxane leveling agent, and Guangdong Jiaming CM-306, BASF

SL 3239.

In the present invention, organic solvents are added to the coating solutions of both coating layers, and alcohols (such as ethanol, propanol, etc.), esters (such as butyl acetate, ethyl acetate, etc.), ketones (such as butanone, acetone) can be selected as single solvents or mixed solvents.

The wetting dispersant in the second anti-glare hardening coating of the present invention can be a polyurethane dispersant, such as BYK DISPERBYK-170TF and DISPERBYK-174; or an acrylic dispersant, such as BYK DISPERBYK-2026 and DISPERBYK-2025.

The transparent support in the present invention is one of triacetate cellulose film (TAC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA) or polyimide (PI), and has a thickness of 40 to 125 μm.

The present invention will be further described below in conjunction with the embodiments.

Example 1

The first coating liquid is composed of the following components by weight:

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

Mixed solvent: 63.62g

30 g of polyurethane (DIC Corporation PANDEX P-910), 1.5 g of polyurethane acrylate (CN997), 0.9 g of isophorone diamine (BASF IPDA), 0.08 g of photoinitiator (BASF Irgacure TPO), 2.9 g of first organic particles (Sekisui Chemical Co., Ltd. MBX-12, monodisperse PMMA 12 μm), 1.0 g of acrylic leveling agent (Guangdong Jiaming CM-703) and 63.62 g of ethyl acetate/butanone 1:1 mixed solvent were poured into a beaker, first stirred at a low speed of 300 rpm for 10 min, then stirred at a high speed of 1000 rpm for 60 min, and stirred evenly to obtain a first coating solution.

The second coating liquid is composed of the following components by weight:

Sartomer CN 997: 35g

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: 61.15 g

35 g of polyurethane acrylate (Sartomer CN 997), 1.5 g of photoinitiator (BASF Irgacure TPO), 0.8 g of silicone leveling agent (Guangdong Jiaming CM-306), 0.5 g of wetting and dispersing agent (DISPERBYK-170TF), 1.4 g of second organic particles (Soken Chemical BXS-500, monodisperse PBMA 5 μm), 0.35 g of zinc oxide nanoparticles and 61.15 g of ethyl acetate/butanone 1:1 mixed solvent were poured into a beaker, first stirred at a low speed of 300 rpm for 10 min, then stirred at a high speed of 1000 rpm for 60 min, and stirred evenly to obtain a second coating solution.

The steps for preparing the zinc oxide nanoparticles are as follows: 1) 40 mL of cyclohexane and 1.5 mL of emulsifier polyglycerol ricinoleate are added to a flask, and the cyclohexane oil phase is dispersed by magnetic stirring; 2 mL of ionized water and azoisobutylcyanamide are added to a beaker, and a small amount of NaOH is added after mixing evenly, and the pH is adjusted to 6-8 to obtain a water phase. The water phase is slowly added to the flask containing the oil phase, and ultrasonic treatment is performed at room temperature for emulsification for 30 minutes to obtain a uniform and stable cyclohexane-water oil-in-water emulsion. 2) Pour 7.8g _ZnCl2 into a three-necked flask, treat ZnCl2 with _SOCl2 by reflux drying _, remove the residual _SOCl2 in the flask in vacuum, slowly drop 20.7g _CH3MgI n- _Bu2O solution into the flask while stirring vigorously, cool and reflux at 70°C for 50 hours, obtain dimethyl zinc by distillation in the temperature range of 130-160°C, dissolve the obtained dimethyl zinc in toluene solvent, drop 3.5g ethanol, stir the solution at room temperature for 12 hours, remove toluene by vacuum drying, obtain a white solid, wash and dry with cyclohexane to obtain isopropanol methyl zinc precursor. 3) Dissolve the isopropanol methyl zinc precursor in cyclohexane, fully disperse it, and then slowly add it to the emulsion. When the concentration of the precursor in the cyclohexane oil phase reaches saturation, the precursor will diffuse to the oil-water interface to form zinc oxide nanoparticles, and a triangular prism crystal structure is obtained under the action of different coordinated oxygen of the ether group and the alcohol group. Disperse the water layer and the oil layer by centrifugation, and then filter the water layer to obtain zinc oxide nanoparticles.

The first coating liquid was coated on one side of a 60um triacetate cellulose film (TAC), placed in an oven at 80°C for 3 minutes, and then placed in an oven at 100°C for curing for 2 minutes to obtain a first coating. The second coating liquid was then coated on the surface of the first coating, placed in an oven at 80°C for 3 minutes, and then cured with UV energy of 450mJ/ ^cm2 to 780mJ/ ^cm2 to obtain a second coating, and an anti-fog and anti-glare hardened film was obtained, wherein L1=7μm and L2=8μm.

Example 2

The first coating liquid is composed of the following components by weight:

OD-X-2195: 40g

Cyanotec EB 2220: 3.0g

Thermal curing agent: 3.5g

Lencolo 5020: 0.3g

SSX-110: 6.2g

BYK-358N: 1.5g

Mixed solvent: 45.5g

40 g of polyurethane (DIC Corporation OD-X-2195), 3.0 g of polyurethane acrylate (Cyanote EB 2220), 0.9 g of isophorone diamine (BASF IPDA), 0.3 g of photoinitiator (Lencolo 5020), 6.2 g of first organic particles (SSX-110, monodisperse MMA 10 μm), 1.0 g of acrylic leveling agent (BYK-358N) and 45.5 g of ethyl acetate/butanone 1:1 mixed solvent were poured into a beaker, first stirred at a low speed of 300 rpm for 10 min, then stirred at a high speed of 1000 rpm for 60 min, and stirred evenly to obtain a first coating solution.

The second coating liquid is composed of the following components by weight:

Cyanotec EB 2220: 40g

Lencolo 5020: 4.5g

BASF Efka SL 3239: 1.5g

DISPERBYK-170TF: 1.3g

Sekisui Chemical Co., Ltd. SSX-108: 3.25g

Zinc oxide nanoparticles: 1.2

Mixed solvent: 48.25g

40 g of polyurethane acrylate (Cyanote EB 2220), 4.5 g of photoinitiator (Lencolo 5020), 1.5 g of siloxane leveling agent (BASF Efka SL 3239), 1.3 g of wetting and dispersing agent (DISPERBYK-170TF), 3.25 g of second organic particles (SSX-108, monodisperse MMA 8 μm, Sekisui Chemical Co., Ltd.), 1.2 g of zinc oxide nanoparticles and 48.25 g of 1:1 mixed solvent of ethyl acetate/butanone were poured into a beaker, first stirred at a low speed of 300 rpm for 10 min, then stirred at a high speed of 1000 rpm for 60 min, and stirred evenly to obtain a second coating solution.

The steps for preparing the zinc oxide nanoparticles are as described in Example 1. The coating method and curing method are as described in Example 1, and the coating thickness L1 = 6 μm, L2 = 9 μm.

Example 3

The first coating liquid is composed of the following components by weight:

Thermosetting resin: 45g

Changxing 6145-100: 3.5g

Thermal curing agent: 4.0g

IGM Omnirad 819: 0.3g

MBX-8: 5.8g

BYK-371: 2.5g

Mixed solvent: 38.9g

Pour 45g of polyurethane (DIC Corporation PANDEX P-910), 3.5g of polyurethane acrylate (Changxing 6145-100), 4.0g of isophorone diamine (BASF IPDA), 0.3g of photoinitiator (IGM Omnirad819), 7.2g of first organic particles (MBX-8, monodisperse PMMA 8μm), 2.5g of acrylic leveling agent (BYK-371) and 38.9g of 1:1 mixed solvent of ethyl acetate/butanone into a beaker, stir at a low speed of 300rpm for 10min, then stir at a high speed of 1000rpm for 60min, and stir evenly to obtain a first coating solution.

The second coating liquid is composed of the following components by weight:

Changxing 6145-100: 55g

IGM Omnirad 819: 6g

Guangdong Jiaming CM-306: 1.8g

DISPERBYK-2025: 1.7g

Soken Chemical MX-180TA: 1.35g

Zinc oxide nanoparticles: 0.8g

Mixed solvent: 33.35g

55 g of polyurethane acrylate (Changxing 6145-100), 6 g of photoinitiator (IGM Omnirad 819), 1.8 g of siloxane leveling agent (Guangdong Jiaming CM-306), 1.7 g of wetting and dispersing agent (DISPERBYK-2025), 1.35 g of second organic particles (Zongyan Chemical MX-180TA, monodisperse PMAA2 μm), 0.8 g of zinc oxide nanoparticles and 33.35 of ethyl acetate/butanone 1:1 mixed solvent were poured into a beaker, first stirred at a low speed of 300 rpm for 10 min, then stirred at a high speed of 1000 rpm for 60 min, and stirred evenly to obtain a second coating solution.

The steps for preparing the zinc oxide nanoparticles are as described in Example 1. The coating method and curing method are as described in Example 1, and the coating thickness L1 = 5 μm, L2 = 4 μm.

Example 4

The first coating liquid is composed of the following components by weight:

Thermosetting resin: 35g

Cytec EB 5129: 2.5g

Thermal curing agent: 2.8g

Lencolo 5020: 0.175g

MBX-8 (monodisperse PMMA 8 μm): 4.48 g

BYK-371: 2.05g

Mixed solvent: 52.995g

Pour 35 g of polyurethane (DIC Corporation PANDEX P-910), 2.5 g of polyurethane acrylate (Cyanote EB 5129), 2.8 g of isophorone diamine (BASF IPDA), 0.175 g of photoinitiator (Lencolo 5020), 4.0 g of first organic particles (SEKISUI CHEMICAL Co., Ltd. MBX-8, monodisperse PMMA 8 μm), 2.05 g of acrylic leveling agent (BYK-371) and 52.995 g of mixed solvent into a beaker, stir at a low speed of 300 rpm for 10 min, then stir at a high speed of 1000 rpm for 60 min, and stir evenly to obtain a first coating solution.

The second coating liquid is composed of the following components by weight:

Cytec EB 5129: 50g

Lencolo 5020: 5.0g

BASF Efka SL 3239: 1.7g

DISPERBYK-2025: 1.65g

Sekisui Chemical Co., Ltd. SSX-105: 1.225g

Zinc oxide nanoparticles: 1.2g

Mixed solvent: 39.225g

50 g of polyurethane acrylate (Cyanote EB 5129), 5.0 g of photoinitiator (Lencolo 5020), 1.7 g of siloxane leveling agent (BASF Efka SL 3239), 1.65 g of wetting and dispersing agent (DISPERBYK-2025), 1.225 g of second organic particles (SSX-105, monodisperse MMA 5 μm, Sekisui Chemical Co., Ltd.), 1.2 g of zinc oxide nanoparticles and 39.255 g of mixed solvent were poured into a beaker, first stirred at a low speed of 300 rpm for 10 min, then stirred at a high speed of 1000 rpm for 60 min, and stirred evenly to obtain a second coating solution.

The steps for preparing the zinc oxide nanoparticles are as described in Example 1. The coating method and curing method are as described in Example 1, and the coating thickness L1 = 5 μm, L2 = 6 μm.

Comparative Example 1

The first coating liquid is composed of the following components by weight:

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

Mixed solvent: 63.62g

30 g of polyurethane (DIC Corporation PANDEX P-910), 1.5 g of polyurethane acrylate (CN997), 0.9 g of isophorone diamine (BASF IPDA), 0.08 g of photoinitiator (BASF Irgacure TPO), 2.9 g of first organic particles (Soken Chemical BXS-500, monodisperse PBMA 5 μm), 1.0 g of acrylic leveling agent (Guangdong Jiaming CM-703) and 63.62 g of ethyl acetate/butanone 1:1 mixed solvent were poured into a beaker, first stirred at a low speed of 300 rpm for 10 min, then stirred at a high speed of 1000 rpm for 60 min, and stirred evenly to obtain a first coating solution.

The second coating liquid is composed of the following components by weight:

Sartomer CN 997: 35g

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: 61.15 g

35 g of polyurethane acrylate (Sartomer CN 997), 1.5 g of photoinitiator (BASF Irgacure TPO), 0.8 g of silicone leveling agent (Guangdong Jiaming CM-306), 0.5 g of wetting and dispersing agent (DISPERBYK-170TF), 1.4 g of second organic particles (Soken Chemical BXS-500, monodisperse PBMA 5 μm), 0.35 g of zinc oxide nanoparticles and 61.15 g of ethyl acetate/butanone 1:1 mixed solvent were poured into a beaker, first stirred at a low speed of 300 rpm for 10 min, then stirred at a high speed of 1000 rpm for 60 min, and stirred evenly to obtain a second coating solution.

The steps for preparing the zinc oxide nanoparticles are as described in Example 1. The coating method and curing method are as described in Example 1, and an anti-fog and anti-glare hardened film is obtained, and the coating thickness L1=7 μm and L2=8 μm.

Comparative Example 2

The first coating liquid is composed of the following components by weight:

OD-X-2195: 40g

Cyanotec EB 2220: 3.0g

Thermal curing agent: 3.5g

Lencolo 5020: 0.3g

SSX-110: 6.2g

BYK-358N: 1.5g

Mixed solvent: 45.5g

40 g of polyurethane (DIC Corporation OD-X-2195), 3.0 g of polyurethane acrylate (Cyanote EB 2220), 0.9 g of isophorone diamine (BASF IPDA), 0.3 g of photoinitiator (Lencolo 5020), 6.2 g of first organic particles (SSX-110, monodisperse MMA 10 μm), 1.0 g of acrylic leveling agent (BYK-358N) and 45.5 g of ethyl acetate/butanone 1:1 mixed solvent were poured into a beaker, first stirred at a low speed of 300 rpm for 10 min, then stirred at a high speed of 1000 rpm for 60 min, and stirred evenly to obtain a first coating solution.

The second coating liquid is composed of the following components by weight:

Cyanotec EB 2220: 40g

Lencolo 5020: 4.5g

BASF Efka SL 3239: 1.5g

DISPERBYK-170TF: 1.3g

Sekisui Chemical Co., Ltd. SSX-108: 3.25g

Commercially available zinc oxide nanoparticles: 1.2 g

Mixed solvent: 48.25g

40 g of polyurethane acrylate (Cyanote EB 2220), 4.5 g of photoinitiator (Lencolo 5020), 1.5 g of siloxane leveling agent (BASF Efka SL 3239), 1.3 g of wetting and dispersing agent (DISPERBYK-170TF), 3.25 g of second organic particles (SSX-108, monodisperse MMA 8 μm, Sekisui Chemical Co., Ltd.), 1.2 g of commercially available zinc oxide nanoparticles (Aladdin reagent, 99%, particle size ≤ 100 nm), and 48.25 g of ethyl acetate/butanone 1:1 mixed solvent were poured into a beaker, first stirred at a low speed of 300 rpm for 10 min, then stirred at a high speed of 1000 rpm for 60 min, and stirred evenly to obtain a second coating solution.

The steps for preparing the zinc oxide nanoparticles are as described in Example 1. The coating method and curing method are as described in Example 1, and the coating thickness L1 = 6 μm, L2 = 9 μm.

The performance of the hardened films prepared in the above examples and comparative examples was tested, and the test results are shown in Table 1.

Table 1 Hardening film performance test results

(1) Light transmittance

The haze transmittance was measured using a haze meter (Nippon Denshoku Corporation; model NDH2000N).

(2) Roughness

The surface and roughness of the samples were tested using a 3D laser microscope (KEYENCE, model VK-X3050).

(3) Glossiness

The glossiness of the sample at 60° was tested using a gloss meter (3ns, model: NHG60M).

(4) Anti-fog

With reference to the rapid thermal fog method in the three standard test methods in standard GB/T 1.1-2009, the anti-fog test was carried out on the experimental samples. The anti-fog levels are divided into 1: completely transparent without water droplets, the clarity of the eye chart is exactly the same as before the test; 2: good clarity, with a small amount of uneven large water droplets; the clarity of more than 50% of the area of the eye chart is exactly the same as before the test; 3: basically transparent, with more water droplets, and the letters and letters of the eye chart are deformed; 4: translucent, with many small water droplets, a small amount of 0.1 below the eye chart is visible; 5: completely opaque, the eye chart is completely invisible.

According to the data of Examples 1 to 4 in Table 1, (1) by controlling the coating thickness and due to the combination of the first organic particles in the first layer and the second organic particles in the second coating, the hardened film of the present invention can achieve effective hardening protection while, on the one hand, having a good control over the haze. For example, in Example 3, the particle size of the second organic particles is as small as 2 μm, but through the first layer of the first organic particles and the thickness of the two coatings, a relatively high haze (20.08%) can 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 a relatively high haze, the gloss (60°) can be as high as 120, and the roughness can be as low as below 1 μm, which effectively solves the problem of low gloss and high roughness of the high haze protective film. (2) By adding self-made triangular prism-shaped nano zinc oxide particles into the second coating layer, on the one hand, an anti-fog effect is effectively achieved. The anti-fog effect can reach level 2 or above when tested by the rapid thermal fog method; on the other hand, the light transmittance and UV blocking effect are effectively improved. In the embodiment described, the light transmittance reaches more than 91%, and the UV blocking rate of 380nm wavelength can reach up to 81.3%.

By comparing Example 1 with Comparative Example 1, the particle sizes of the first organic particles and the second organic particles in Comparative Example 1 do not meet the relationship of 0＜D1-L1＜L2, D2+D1-L1＞L2, the haze and glossiness are significantly reduced, the roughness is significantly increased, and the anti-fog property is also reduced.

By comparing Example 2 with Comparative Example 2, the zinc oxide nanoparticles used in Comparative Example 2 are commercially available zinc oxide from Aladdin Reagent. The anti-fog property is tested by the rapid thermal fog method, and the anti-fog effect is determined to be level 4. Compared with Example 2, conventional zinc oxide has almost no anti-fog effect, which shows the anti-fog advantage of triangular nano zinc oxide.

Claims (10)

1. An anti-fog and anti-glare hardened film, characterized in that: the hardened film is composed of a transparent support and two layers of anti-glare hardened coatings coated on one side of the transparent support; The first anti-glare hardened coating is obtained by coating and curing a coating solution made of the following components in parts by mass: 30 to 45 parts of a thermosetting resin; UV curing resin: 1.5~3.5; Photoinitiator: 0.08～0.3; Thermal curing agent: 0.9～4.0; First organic particles: 2.9-6.2; Leveling agent: 1.0～2.5; Solvent: 38.9～63.62; The second anti-glare hardened coating is formed by coating and curing a coating solution made of the following components in parts by mass: UV curable resin: 35-55; Photoinitiator: 1.5～6; Leveling agent: 0.8～1.8; Wetting and dispersing agent: 0.5～1.7; Second organic particles: 0.7-3.25; Zinc oxide nanoparticles: 0.35-1.2; Solvent: 33.35～61.15. 2. The anti-fog and anti-glare hardened film according to claim 1 is characterized in that: the particle size of the first organic particles is D1 = 5~12μm, the particle size of the second organic particles is D2 = 2~8μm, and both are monodisperse organic particles; the thickness of the first anti-glare hardened coating is L1, and the thickness of the second anti-glare hardened coating is L2, and L1, L2, D1, and D2 satisfy the following relationship: 0＜D1-L1＜L2, D2+D1-L1＞L2. 3 . The anti-fog and anti-glare hardened film according to claim 1 , wherein the zinc oxide nanoparticles are in the shape of triangular prisms and have a particle size of 50 to 120 nm. 4. The anti-fog and anti-glare hardened film according to claim 3, characterized in that: the zinc oxide nanoparticles are prepared by a microemulsion method, and the preparation steps are as follows: a. Preparation of cyclohexane-water oil-in-water emulsion: 40 mL of cyclohexane and 1.5 mL of emulsifier polyglycerol ricinoleate were added to a flask, and the cyclohexane oil phase was dispersed by magnetic stirring; 2 mL of deionized water and azoisobutylcyanamide were added to a beaker, and a small amount of NaOH was added after mixing evenly, and the pH was adjusted to 6-8 to obtain an aqueous phase; the aqueous phase was slowly added to the flask containing the oil phase, and the emulsification was rapidly stirred for 30 minutes at room temperature to obtain a uniform and stable cyclohexane-water oil-in-water emulsion; the head group ether group and alcohol group in the emulsifier polyglycerol ricinoleate were concentrated at the oil-water interface; b. Preparation of methyl zinc isopropoxide precursor: 7.8 g _ZnCl2 was poured into a three-necked flask, and ZnCl2 was treated with _SOCl2 by reflux drying _. The residual _SOCl2 in the flask was removed in vacuum, and 20.7 g _CH3MgI n- _Bu2O solution was slowly added dropwise into the flask while stirring vigorously. After cooling and refluxing at 70°C for 50 hours, dimethyl zinc was obtained by distillation in the temperature range of 130-160°C. The obtained dimethyl zinc was dissolved in toluene solvent, and 3.5 g ethanol was added dropwise. The solution was stirred at room temperature for 12 hours, and toluene was removed by vacuum drying to obtain a white solid, which was then washed and dried with cyclohexane to obtain a methyl zinc isopropoxide precursor; c. Formation of zinc oxide nanoparticles: dissolve the isopropanol methyl zinc precursor in cyclohexane solvent, fully disperse it, and then slowly add it dropwise to the cyclohexane-water oil-in-water emulsion. When the concentration of the isopropanol methyl zinc precursor in the cyclohexane oil phase reaches saturation, the isopropanol methyl zinc precursor will diffuse to the oil-water interface to form zinc oxide nanoparticles, and a triangular prism crystal structure is obtained under the action of different coordinated oxygens of the ether group and the alcohol group; d. Centrifugally disperse the water layer and the oil layer, and then filter the water layer to obtain zinc oxide nanoparticles. 5. The anti-fog and anti-glare hardened film according to claim 1 is 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, polybutyl methacrylate, methyl methacrylate or polymethyl methacrylate. 6. The anti-fog and anti-glare hardened film according to claim 1 is characterized in that: the thermosetting resin used in the first anti-glare hardening coating is polyurethane with a molecular weight of 1000 to 6000; the UV curing resin is polyurethane acrylate with a functionality of 6 to 9; the mass of the UV curing resin is not higher than 8% of the mass of the thermosetting resin, and the first anti-glare hardening coating is thermally cured at 100 to 120°C for 2 to 5 minutes to completely cure the thermosetting resin. 7 . The anti-fog and anti-glare hardened film according to claim 1 , wherein the UV curable resin in the second anti-glare hardened coating layer is a polyurethane acrylate with a functionality of 6 to 9. 8. The anti-fog and anti-glare hardened film according to claim 1, characterized in that: the leveling agent in the first anti-glare hardened coating layer is an acrylic leveling agent; the leveling agent in the second anti-glare hardened coating layer is a silicone leveling agent. 9. The anti-fog and anti-glare hardened film according to claim 1 is characterized in that the transparent support is one of triacetate cellulose film (TAC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA) or polyimide (PI), and its thickness is 40 to 125 μm. 10. The anti-fog and anti-glare hardened film according to claim 1, characterized in that the coating method of the first anti-glare hardened coating layer and the second anti-glare hardened coating layer is one of roller coating, blade coating, rod coating, or gravure coating.

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