CN114895386B - Anti-glare film, manufacturing method and mold manufacturing method - Google Patents

Anti-glare film, manufacturing method and mold manufacturing method Download PDF

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Publication number
CN114895386B
CN114895386B CN202210383493.6A CN202210383493A CN114895386B CN 114895386 B CN114895386 B CN 114895386B CN 202210383493 A CN202210383493 A CN 202210383493A CN 114895386 B CN114895386 B CN 114895386B
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film
mass
mixture
parts
curing
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CN114895386A (en
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陈飞
詹兴华
贺本芳
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Shenzhen Nahongyi Optical Technology Co ltd
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Shenzhen Nahongyi Optical Technology Co ltd
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11Anti-reflection coatings
    • G02B1/111Anti-reflection coatings using layers comprising organic materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00Producing flat articles, e.g. films or sheets
    • B29D7/01Films or sheets
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

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  • General Physics & Mathematics (AREA)
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  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Optical Elements Other Than Lenses (AREA)

Abstract

The invention discloses an anti-dazzle film, a manufacturing method and a mold manufacturing method, wherein the anti-dazzle film comprises a photo-curing mixture and a thermosetting mixture; the photo-curing mixture comprises a resin prepolymer, a reactive monomer, a photoinitiator and a leveling agent; the components of the thermosetting mixture comprise resin prepolymer, thermosetting agent, catalyst, solvent, anchoring material and other auxiliary agents; the proportion of the photo-setting mixture and the thermosetting mixture is 5% -25%. The anti-glare film solves the technical problems of low contrast and flash point of the anti-glare film in the prior art.

Description

Anti-glare film, manufacturing method and mold manufacturing method
Technical Field
The invention relates to the technical field of anti-glare films, in particular to an anti-glare film, a manufacturing method and a mold manufacturing method.
Background
In life, electronic products, particularly high resolution (greater than 400ppi resolution) display electronic products, are indispensable for people's work and life. The comfort of use and the impact on visual health are one of the key points in competition for display-type products. Therefore, the high resolution display devices are all introduced with anti-reflection and anti-dazzle functional films so as to reduce glare caused by external light intensity reflection and glare caused by light scattering in the devices.
At present, anti-glare films are classified into several categories: 1. forming an irregular rough structure on the surface by spraying silica gel; 2. particles are introduced into the anti-glare coating liquid, and convex-concave structures are formed on the surface by using the fact that the particles are larger than the thickness of the film or irregular concave-convex structures are formed on the surface by using the inducibility of the particles. The anti-glare film is prepared by controlling particles to be uniformly dispersed through a technology, and inducing the surface of the film to form a concave-convex structure, so that reflection can be reduced, but the size of the concave-convex structure is uncontrollable, and a flash point can be generated in high-resolution display. 3. The surface energy (fluorine and silicon) is utilized, the solvent volatilizes to form the bennett cells to form the concave-convex structure, and the requirement on the solvent selection is high. 4. The phase separation is formed by utilizing the difference of two or more polymer properties to form a concave-convex structure.
The anti-dazzle film formed by the existing anti-dazzle coating liquid containing particles simultaneously utilizes surface roughness to reduce the interaction of external light reflection light and internal particles and resin with different refractive indexes to form haze. However, the antiglare film prepared by this technique is difficult to have high contrast, and has a problem of flash point (Sparkling).
Disclosure of Invention
The invention aims to provide an anti-glare film, a manufacturing method and a mold manufacturing method, and solves the technical problems of low contrast and flash point of the anti-glare film in the prior art.
In order to achieve the above object, the present invention proposes an antiglare film comprising a photocurable mixture and a thermosetting mixture;
the photo-curing mixture comprises a resin prepolymer, a reactive monomer, a photoinitiator and a leveling agent;
the components of the thermosetting mixture comprise resin prepolymer, thermosetting agent, catalyst, solvent, anchoring material and other auxiliary agents;
the proportion of the photo-setting mixture and the thermosetting mixture is 5% -25%.
Optionally, the anti-glare film comprises the following components in percentage by weight:
5% -20% of resin prepolymer;
10% -60% of active monomer;
0.2% -5% of photoinitiator;
5% -20% of the heat curing agent;
the catalyst comprises: 0.5% -3%;
the leveling agent comprises: 0.01% -2%;
8% -25% of anchoring material;
30% -70% of solvent;
0.5 to 2 percent of other auxiliary agents.
Optionally, the resin prepolymer comprises a photocurable prepolymer containing carbon-carbon double bonds, and the components of the photocurable mixture comprise:
photo-curing prepolymer containing carbon-carbon double bonds: 5% -20%;
5-80% of active monomer;
0.2 to 5 percent of photoinitiator;
leveling agent: 0.01 to 2 percent.
Optionally, the resin prepolymer comprises epoxy resin oligomer and phenolic resin, the catalyst is a toughening agent, the anchoring material is nano particles, and the components of the thermosetting mixture comprise:
5 to 20 percent of epoxy resin oligomer;
5-20% of phenolic resin;
toughening agent: 1% -10%;
5% -20% of a thermosetting agent;
5% -20% of nano particles;
30-70% of solvent;
0.5 to 2 percent of other auxiliary agents.
The invention also provides a manufacturing method of the anti-dazzle film, which is used for manufacturing the anti-dazzle film, and comprises the following steps:
determining a first preset proportion of the photo-curing mixture and a second preset proportion of the thermosetting mixture according to the proportion of the photo-curing mixture of the anti-glare film and the thermosetting mixture of the anti-glare film and the component content;
configuring a photo-curing mixture according to the first preset proportion;
preparing a thermosetting mixture according to the second preset proportion;
mixing the photo-curing mixture and the thermosetting mixture according to a first preset proportion to form an anti-glare film material composition;
uniformly coating the anti-glare film material composition on a substrate to form an anti-glare film primary product;
introducing a first gas to thermally cure the anti-glare film primary finished product at a first temperature within a first preset time length;
performing light curing on the anti-glare film primary finished product after heat curing for a second preset time length at a first preset light intensity;
and (3) placing the thermally cured and photo-cured anti-glare film primary finished product into plasma for a third preset time length to obtain an anti-glare film finished product.
Optionally, the first preset ratio is: 15 parts by mass of polyester acrylate prepolymer, 5 parts by mass of epoxy acrylate prepolymer, 10 parts by mass of dipentaerythritol hexaacrylate, 35 parts by mass of trimethylolpropane triacrylate, 31.5 parts by mass of tripropylene glycol diacrylate, 3 parts by mass of photoinitiator (819) and 0.5 part by mass of flatting agent.
Optionally, the step of configuring the photocurable mixture according to the first preset formulation includes:
15 parts by mass of polyester acrylate prepolymer, 5 parts by mass of epoxy acrylate prepolymer, 10 parts by mass of dipentaerythritol hexaacrylate, 35 parts by mass of trimethylolpropane triacrylate and 31.5 parts by mass of tripropylene glycol diacrylate are weighed, mixed at a speed of 120-130 r/min for 30 minutes, 3 parts by mass of photoinitiator (819) is weighed, 0.5 part by mass of flatting agent is added into the mixture, the mixture is continuously stirred at a speed of 120-130 r/min for 15 minutes, and static defoaming is carried out.
Optionally, the second preset ratio is: 15 parts by mass of 10-nanometer-particle-size metal oxide nanoparticles are dispersed in 51.9 parts by mass of ethyl acetate, 1-methoxy-2-propanol, methyl ethyl ketone, a xylene mixed solvent, 3 parts by mass of epoxy resin oligomer, 1210 parts by mass of epoxy resin oligomer, 68 parts by mass of phenolic resin ethylene glycol diglycidyl ether, 2.1 parts by mass of a toughening agent, 5 parts by mass of a curing agent 4,4' -Diamino Diphenyl Sulfone (DDS), and 5 parts by mass of an accelerator 2-methylimidazole (accounting for 0.1% of the epoxy resin).
Optionally, the step of configuring the thermosetting mixture according to the second preset ratio includes:
15 parts by mass of metal oxide nanoparticles with the particle size of 10 nanometers are weighed and dispersed in 51.9 parts by mass of mixed solvent of ethyl acetate, 1-methoxy-2-propanol, methyl ethyl ketone and xylene, and the mixture is subjected to ultrasonic dispersion for 15 minutes to form light blue clear liquid. 3 parts by mass of epoxy resin oligomer is added, the speed is 120r/min-130r/min, and the stirring time is 120 min, so that the epoxy resin oligomer is modified and coated on the surface of the nano particle. Then weighing 1210 parts by mass of epoxy resin oligomer, 68 parts by mass of phenolic resin ethylene glycol diglycidyl ether and 2.1 parts by mass of flexibilizer, continuously stirring and mixing for 60 minutes, then adding 5 parts by mass of curing agent 4,4' -diaminodiphenyl sulfone (DDS), and 5 parts by mass of accelerator 2-methylimidazole (accounting for 0.1% of epoxy resin) and other auxiliary agents, continuously stirring for 15 minutes, and standing for later use.
Optionally, the step of uniformly coating the anti-glare film material composition on a substrate to form an anti-glare film primary product includes:
setting the rotating speed of the spin coater to 300r/min;
the anti-glare film material composition was coated onto a 250 μm thick PET substrate to form an anti-glare film primary product.
Optionally, the first preset ratio is 1:8 or 1:20 or 1:8 or 1:10.
The invention also provides a manufacturing method of the anti-dazzle film die, which comprises the following steps:
aging the anti-glare film primary finished product manufactured by the manufacturing method of the anti-glare film to obtain an anti-glare film die;
carrying out UV transfer printing on the anti-dazzle film die to obtain an anti-dazzle structure film;
coating a UV glue solution on the transferred anti-glare structure film to realize UV curing;
and aging the anti-glare structure film to obtain the anti-glare film mold.
The antiglare film of the present invention comprises a photocurable mixture and a thermally curable mixture; the photo-curing mixture comprises a resin prepolymer, an active monomer, a photoinitiator and a leveling agent; the components of the thermosetting mixture comprise resin prepolymer, thermosetting agent, catalyst, solvent, anchoring material and other auxiliary agents; the proportion of the photo-setting mixture and the thermosetting mixture is 5% -25%. Through the scheme, the components of the anti-dazzle film are improved and divided into a photo-curing mixture and a thermosetting mixture, then the photo-curing mixture and the thermosetting mixture are respectively matched with different formulas, and finally the photo-curing mixture and the thermosetting mixture are mixed according to a special proportion, so that the anti-dazzle film with the components has the characteristics of high transmittance and high contrast ratio, and has no flash point in high-pixel resolution display. Thus solving the technical problems of low contrast and flash point of the anti-glare film in the prior art.
Drawings
The invention is further described below with reference to the drawings and examples;
FIG. 1 is a schematic product diagram of an antiglare film in one embodiment.
FIG. 2 is a flow chart of a method for manufacturing an anti-glare film according to an embodiment.
Detailed Description
Reference will now be made in detail to the present embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein the accompanying drawings are used to supplement the description of the written description so that one can intuitively and intuitively understand each technical feature and overall technical scheme of the present invention, but not to limit the scope of the present invention.
The invention provides an anti-dazzle film, a manufacturing method and a mold manufacturing method, and aims to solve the technical problems of low contrast and flash point of the anti-dazzle film in the prior art.
In one embodiment, an antiglare film is disclosed that includes a photocurable mixture and a thermally curable mixture; the photo-curing mixture comprises a resin prepolymer, a reactive monomer, a photoinitiator and a leveling agent;
the components of the thermosetting mixture comprise resin prepolymer, thermosetting agent, catalyst, solvent, anchoring material and other auxiliary agents; the proportion of the photo-setting mixture and the thermosetting mixture is 5% -25%.
The components of the anti-dazzle film are improved through the scheme, the anti-dazzle film is divided into a photo-curing mixture and a thermosetting mixture, a dual curing scheme is adopted, different formulas are respectively matched with the anti-dazzle film and the thermosetting mixture, finally the anti-dazzle film and the thermosetting mixture are mixed according to a special proportion, the proportion of the photo-curing mixture and the thermosetting mixture is controlled to be 5% -25%, and the anti-dazzle film produced according to the proportion is shown in the figure 1, has the characteristics of high transmittance and high contrast, and has no flash point in high-pixel resolution display. Thus solving the technical problems of low contrast and flash point of the anti-glare film in the prior art.
In one embodiment, the antiglare film comprises the following components:
5% -20% of resin prepolymer;
10% -60% of active monomer;
0.2% -5% of photoinitiator;
5% -20% of the heat curing agent;
the catalyst comprises: 0.5% -3%;
the leveling agent comprises: 0.01% -2%;
8% -25% of anchoring material;
30% -70% of solvent;
0.5 to 2 percent of other auxiliary agents.
Through the scheme, the content of each component can be further limited, the unbalance of the component content caused by excessive single components or single pursuing proportion is avoided, the difficulty of industrial screening of specific proportions can be further reduced, the formula can be flexibly changed according to the price of raw materials or the difficulty in obtaining within the defined parameter range, and the better effect can be realized when the precision range is lower. The total content of the components of the antiglare film was 100%.
Alternatively, among the components of the antiglare film, the resin prepolymer includes a photocurable prepolymer having a carbon-carbon double bond and an epoxy resin oligomer, and the reactive monomer includes a reactive monomer having a carbon-carbon double bond and an epoxy reactive monomer. The thermosetting agent is polyamine curing agent. The catalyst is an acid catalyst. The anchoring material refers to nanoparticles with surface modified polymerizable functional groups. Titanium oxide, zirconium oxide, and silicon oxide are preferable.
Optionally, the resin prepolymer may be mixed with one of the following contents: 5% -10%; 10% -15%; 15% -20%.
Optionally, the reactive monomer may be mixed according to one of the following contents: 10% -20%; 20% -30%; 30% -40%; 40% -50%; 50% -60%.
Optionally, the photoinitiator may be mixed with one of the following contents: 0.2% -1%; 1% -2%; 2% -3%; 3% -4%; 4% -5%.
Optionally, the thermosetting agent may be mixed with one of the following contents: 5% -10%; 10% -15%; 15% -20%.
Optionally, the catalyst can be prepared from one of the following components: 0.5 to 1 percent; 1% -2%; 2% -3%.
Optionally, the leveling agent may be mixed with one of the following contents: 0.01 to 0.5 percent; 0.5 to 1 percent; 1 to 1.5 percent; 1.5 to 2 percent.
Optionally, the anchoring material can be selected from one of the following contents of 8% -10%; 10% -15%; 15% -20%; 20% -25%.
Optionally, the solvent can be selected from one of the following contents of 30% -40%; 40% -50%; 50% -60%; 60% -70%.
Optionally, the other auxiliary agents can be selected from one of the following contents of 0.5% -1%; 1 to 1.5 percent; 1.5 to 2 percent.
The proportion is selected by following the principle that the proportion of the photo-curing mixture and the thermosetting mixture is 5% -25%, and the range can be finely adjusted according to the principle so as to ensure that the photo-curing mixture and the thermosetting mixture fall in the content of the components of the anti-glare film.
In an alternative embodiment, the resin prepolymers include UV light curable (free radical) prepolymers and thermally curable epoxy resins.
The UV light-cured prepolymer is a resin containing carbon-carbon unsaturated double bonds, and comprises unsaturated polyester, polyurethane acrylate resin, epoxy acrylate resin, polyester acrylate and polyether acrylate resin, acrylated acrylate resin, organic silicon acrylate resin and the like. When the proportioning of the materials is carried out, one or more of the materials can be selected to be mixed to realize the UV light curing prepolymer. It should be noted that, preferably, the UV light-cured prepolymer is polyurethane acrylate resin, the viscosity range is 10000-20000 mpa.s, which can realize better viscosity and ensure the structural stability after curing.
The prepolymer to be cured by heating is an epoxy resin, and includes a glycidyl ether type epoxy resin, a bisphenol a type epoxy resin, and the like.
In an alternative embodiment, the reactive monomer comprises an organic molecule containing a carbon-carbon unsaturated double bond, including vinyl-containing aliphatic compounds, vinyl-containing aromatic compounds, at least one of acrylic anhydride compounds, methacrylic anhydride compounds, and the like, while the reactive monomer further comprises an organic molecule containing an epoxy functional group, including but not limited to ethylene glycol diglycidyl ether, polyglycidyl ether, propylene oxide butyl ether, propylene oxide phenyl ether, propylene oxide ethyl ether, propylene oxide propyl ether, and the like.
In an alternative embodiment, the initiator includes a photoinitiator initiated by ultraviolet light and a thermosetting agent initiated by heat to open the epoxy ring, wherein the photoinitiator is selected from the group consisting of free radical photoinitiators commonly used such as 369, 819, 84, TPO (C22H 21O2P, trimethylbenzoyl-diphenylphosphine oxide) and the like.
In an alternative embodiment, the thermal curing agent may be a multi-cationic thermal initiator, an anhydride, an imidazole, dicyandiamides such as aliphatic amines, polyamides, alicyclic amines, modified amines, or the like.
In an alternative embodiment, the catalyst refers to an acid catalyst comprising p-toluene sulfonic acid, dodecylbenzene sulfonic acid, hexafluorophosphonic acid, butyl phosphoric acid, derivatives of aromatic phosphates, and various carboxylic acids.
In an alternative embodiment, the anchoring material refers to nanoparticles having surface modifications with polymerizable functional groups. The nanoparticles are preferably, but not limited to, silica, zirconia, titania. The particle size of the contained nano particles is below 0-150nm, and most preferably below 50nm. The surface of the nanoparticle is connected with a modifier through a chemical bond, and the tail end of the modifier is provided with a polymerizable group.
Wherein the nanoparticle can be an inorganic nanoparticle, a polymer-inorganic composite nanoparticle, or a polymer nanoparticle. The particle size of the contained nano particles is below 0-150nm, and most preferably below 50nm. The surface of the nanoparticle is connected with a modifier through a chemical bond, and the tail end of the modifier is provided with an epoxy group.
In an alternative embodiment, the solvent comprises a fatty solvent, an organic alcohol, a lipid, etc., but is not limited thereto, and preferably at least two of ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, xylene, n-butanol, 1-methoxy-2-propanol, ethylene glycol monobutyl ether, etc. are mixed.
In one embodiment, the resin prepolymer comprises a photocurable prepolymer containing carbon-carbon double bonds, and the components of the photocurable mixture comprise:
photo-curing prepolymer containing carbon-carbon double bonds: 5% -20%;
5-80% of active monomer;
0.2 to 5 percent of photoinitiator;
leveling agent: 0.01 to 2 percent.
By the above embodiments, the photo-curing function of the photo-curable mixture can be achieved. The photo-curing prepolymer containing carbon-carbon double bonds can better realize the photo-curing process of the anti-dazzle film, and the anti-dazzle film mixed with the thermosetting mixture has better physical properties through the photoinitiator, the flatting agent and the active monomer. The stability of the components of the anti-glare film material is ensured, and the prepared anti-glare film has consistent microstructure.
In one embodiment, the resin prepolymer comprises epoxy oligomer and phenolic resin, the catalyst is a toughening agent, the anchoring material is nanoparticles, and the components of the thermally curable mixture comprise:
5 to 20 percent of epoxy resin oligomer;
5-20% of phenolic resin;
toughening agent: 1% -10%;
5% -20% of a thermosetting agent;
5% -20% of nano particles;
30-70% of solvent;
0.5 to 2 percent of other auxiliary agents.
By the above embodiment, the heat curing function of the heat curing mixture can be achieved. And the anti-dazzle film mixed with the photo-curing mixture has better physical properties through the toughening agent, the thermosetting agent, the nano particles and the solvent. The stability of the components of the anti-glare film material is ensured, and the prepared anti-glare film has consistent microstructure.
In one embodiment, the anti-glare film can be used as an anti-glare function protective film on LCD screens, LED screens, OLED, QLED, mini LED, micro LED high resolution pixel display screens by coating an anti-fingerprint liquid (AF) on the surface to form an AGAF film or coating a lamination with a low refractive index and a high refractive index to form an AGARAF film by coating an AF liquid.
Wherein, through above-mentioned scheme, can make various function protection film with anti-dazzle membrane in combination with other functions. Can be widely applied to various occasions.
The invention also provides a manufacturing method of the anti-dazzle film, and referring to fig. 2, the manufacturing method of the anti-dazzle film is used for manufacturing the anti-dazzle film, and the manufacturing method of the anti-dazzle film comprises the following steps:
s1, determining a first preset proportion of the photo-curing mixture and a second preset proportion of the thermosetting mixture according to the proportion of the photo-curing mixture of the anti-glare film and the thermosetting mixture of the anti-glare film and the component content;
wherein, based on the antiglare film as described above, the proportion of the photo-setting mixture of the antiglare film and the thermosetting mixture of the antiglare film is 5 to 25%, and the component content is 5 to 20% with reference to the resin oligomer; 10-60% of active monomer; 0.2 to 5 percent of photoinitiator; 5% -20% of a thermosetting agent; catalyst: 0.5% -3%; leveling agent: 0.01% -2%; 8% -25% of anchoring material; 30-70% of solvent; 0.5 to 2 percent of other auxiliary agents. According to the two parameters, a plurality of groups of ratios of the photo-curing mixture and the thermosetting mixture can be obtained, and the ratios are respectively defined as a first preset ratio and a second preset ratio.
It should be noted that, a set of implementation schemes of the photo-curing mixture and the thermosetting mixture are provided in the antiglare film as described above, which are merely for illustrating the possibility of implementation, and the schemes and the detailed contents of the first preset ratio and the second preset ratio at this time are not limited accordingly.
S2, configuring a photo-curing mixture according to the first preset proportion;
s3, preparing a thermosetting mixture according to the second preset proportion;
s4, mixing the photo-curing mixture and the thermosetting mixture according to a first preset proportion to form an anti-glare film material composition;
the first preset proportion is required to fall within 5% -25%, and the conversion ratio is 1:20-1:4, and the anti-glare film material composition is obtained by mixing the first preset proportion.
The antiglare film material composition at this time is only a preliminary material, and a series of treatments are required to be performed subsequently.
S5, uniformly coating the anti-glare film material composition on a substrate to form an anti-glare film primary finished product;
in an alternative embodiment, the step of uniformly coating the anti-glare film material composition on the substrate to form an anti-glare film primary product includes: the spin coater was set at a rotational speed of 300r/min, and the antiglare film material composition was coated on a PET substrate 250 μm thick to form an antiglare film primary product.
Wherein the substrate comprises a sheet or plate of high molecular polymer such as PET (polyethylene terephthalate), PC, PMMA, etc., or glass.
S6, introducing first gas to thermally cure the anti-glare film primary finished product at a first temperature within a first preset time length;
wherein, the heat curing can cure the inner layer, and the photo-curing mixture and the heat curing mixture are mixed in the process, so that the heat curing process is uniformly realized on the anti-glare film primary finished product when the heat curing is carried out at the moment.
Taking an alternative embodiment as an example, carbon dioxide is introduced at the temperature of 80 ℃ to carry out thermal baking and curing, wherein the curing time is 30 minutes, namely, the first temperature is 80 ℃, the first preset time length is 30 minutes, and the first gas is carbon dioxide.
S7, carrying out photo-curing on the anti-glare film primary finished product after heat curing for a second preset time length at a first preset light intensity;
taking an alternative embodiment as an example, taking out the primary anti-glare film finished product after heat curing and irradiating for 7 seconds by using an ultraviolet electrodeless lamp under the protection of nitrogen atmosphere at the first preset light intensity (light intensity). The first preset light intensity needs to be set according to practical situations, and the second preset time length can be set to 7 seconds. It should be noted that the first preset light intensity and the second preset time period may be changed according to circumstances. Or taking out the primary finished product of the anti-glare film after heat curing, and irradiating for 7 seconds by using an ultraviolet electrodeless lamp in a full ultraviolet band under the condition of 1400mW/cm < 2 > light intensity and nitrogen atmosphere protection.
Wherein, in the above process, the purpose of illumination is to cure the resin uv to form different phases. In the foregoing process, the photo-setting mixture and the thermosetting mixture are mixed, and therefore, at the time of photo-setting at this time, the photo-setting process is also uniformly performed on the antiglare film primary product. The internal structure of the antiglare film primary product after heat curing and light curing respectively has been stabilized.
It should be noted that the thermal curing and photo-curing in the steps 6-7 are dual curing, and dual curing refers to a mixed system of free radical photo-initiated curing acrylate and thermal curing epoxy resin, and the photo-initiated wavelength band of the UV resin has different absorption peaks from 200nm to 405 nm. The catalyst catalyzes the mutual linking of the resin material and the anchoring material under the external stimulus (UV illumination and heating), and the macromolecular chain grows out from the anchoring material, so that a 'skeleton' film layer with loose outside and a fold structure inside is formed. The surface structure of the film layer at this time does not have a folded structure of the phase separation AG, and further treatment is required to make the "skeleton" structure stand out, resulting in the structure of the diffraction optical AG.
S8, placing the anti-glare film primary finished product after heat curing and photo-curing into plasma for processing for a third preset time length to obtain an anti-glare film finished product.
The dual-curing system is used for heating to cure the inner layer, the material of the UV system is mixed with the material of the thermosetting system to the surface of the whole material through volatilization of the solvent, and then the surface of the coating is subjected to UV curing through UV photo-curing according to the heat-cured bottom layer structure and the heat-cured material doped in the material of the UV system, so that the surface structure which takes the heat-cured material as a core and is further subjected to UV curing along the surface texture of the heat-cured material is formed. When the cured seed solvent volatilizes, the surface is cured at first to form a bottom layer and then to form a random micro-fold structure on the surface of the film due to different upper and lower curing speeds, and the random micro-fold structure has an anti-dazzle effect. The plasma bombards and removes loose materials on the surface of the primary finished product of the Anti-dazzle film after the prior baking and UV irradiation, so that the lower skeleton structure is exposed, and a milky white film sample with surface texture is obtained, the surface of the sample is provided with a phase separation AG (Anti-glare) structure, the surface of the Anti-dazzle film prepared from the material composition is provided with a random micro-fold structure, wherein the line width of the micro-structure is in the range of 2um to 6um, and the line density is about 65% -80%. In the above embodiment, based on the principle of diffraction optics and the structure of the device, the surface of the manufactured anti-glare film finished product has a random micro-fold structure, and as shown in fig. 1, the effect of high haze is generated, and the high transmittance is achieved. Thus solving the technical problems of low contrast and flash point of the anti-glare film in the prior art.
In an alternative embodiment, the step of placing the thermally cured and photo-cured antiglare film preform into a plasma for a third predetermined length of time to obtain an antiglare film preform includes:
the treated sample was placed in an oxygen plasma for 10 minutes with a vacuum of 10-3Pa, a plasma frequency of 2.45GHz and an intensity of 260W. The oxygen plasma bombards and removes the loose material on the surface of the membrane after the previous heat drying and light irradiation, so that the lower skeleton structure is exposed, and a membrane sample with milky white surface grains is obtained, and the surface of the sample has a phase separation AG structure. Wherein a vacuum environment is required during plasma processing. That is, the chamber is first evacuated to a desired vacuum and then treated by introducing a small amount of oxygen. The frequency and intensity cannot be changed to achieve the AG effect described in this patent. In this case, the loose material is a material portion which cannot be combined with other materials to form a stable and dense structure, and these portions are bombarded and removed in oxygen plasma, so that only a dense structure is left.
Oxygen plasma bombards and removes loose materials on the surface of the primary anti-dazzle film finished product after the previous baking and light irradiation, so that the lower skeleton structure is exposed, and the anti-dazzle film finished product with milky white surface grains is obtained, and the surface of the anti-dazzle film finished product is provided with a phase separation AG structure. When the anti-dazzling film is cured, the upper and lower curing speeds of the anti-dazzling film primary finished product are different due to heat curing and light curing, and aggregation movement of nano particles is caused by products under different curing conditions, such as core particles after heat curing, so that a corrugation-like fluctuation can be formed on the surface of liquid, a light curing rapid surface drying fixed structure is formed, and the surface of the anti-dazzling film finished product is formed into a random micro-fold structure after heating an inner layer for curing.
The particle size of the nanoparticles serving as anchors, which are contained in the photocurable prepolymer and the reactive monomer in the resin prepolymer, affects the structural size of the surface random micro-wrinkles. The content of the photo-curing prepolymer and the active monomer is reduced by 5 percent from 20 percent, and the width dimension of the random microstructure is reduced from 20 to 15 micrometers to 5 to 0.5 micrometers; the smaller the particle diameter of the nanoparticle, the larger the random microstructure size adjustment range. The particle size is too large, the degree of randomness is reduced, the particles tend to be round and convex, and flash points are generated during high-pixel display. Therefore, the particle diameter of the nanoparticles is controlled to be less than 200 nanometers, and optimally to be 1-50 nm. Meanwhile, the surface of the nano particle is modified with a modifier with a polymerizable group, so that the dispersibility of the nano particle in a system is improved, the nano particle is not agglomerated and is not settled, and the particle and the resin material are combined by chemical bonds during polymerization and solidification. The stability of the components of the anti-glare film material is ensured, and the prepared anti-glare film has consistent microstructure.
The haze formed by the random microstructure of the film surface prepared by the anti-dazzle film material composition provided by the invention is 75% -85%, and a light (UV) transfer printing mold can be manufactured based on an anti-dazzle film finished product through a process for preparing the UV transfer printing mold. The UV transfer printing die with different haze can be manufactured by copying, washing and fine-adjusting the depth of the microstructure on the surface of the film. Is convenient for mass production.
Optionally, the step of placing the thermally cured and photo-cured primary anti-glare film product into plasma for a third preset time length to obtain the anti-glare film product further comprises:
coating an anti-fingerprint liquid (AF) on the surface of the anti-dazzle film finished product to prepare an AGAF film; or alternatively, the first and second heat exchangers may be,
coating a coating with low refractive index and high refractive index on the lamination of the anti-dazzle film finished product, and then coating AF liquid to prepare the AGARAF film.
Through the mode, the anti-glare film finished product can be used on LCD screens, LED screens, OLED (organic light emitting diode), QLED (light emitting diode), mini LED and Micro LED high-resolution pixel display screens, namely, the anti-glare function protective film is attached to the anti-glare function protective film.
Optionally, the first preset ratio is: 15 parts by mass of polyester acrylate prepolymer, 5 parts by mass of epoxy acrylate prepolymer, 10 parts by mass of dipentaerythritol hexaacrylate, 35 parts by mass of trimethylolpropane triacrylate, 31.5 parts by mass of tripropylene glycol diacrylate, 3 parts by mass of photoinitiator (819) and 0.5 part by mass of flatting agent.
Optionally, the step of configuring the photocurable mixture according to the first preset formulation includes:
15 parts by mass of polyester acrylate prepolymer, 5 parts by mass of epoxy acrylate prepolymer, 10 parts by mass of dipentaerythritol hexaacrylate, 35 parts by mass of trimethylolpropane triacrylate and 31.5 parts by mass of tripropylene glycol diacrylate are weighed, mixed at a speed of 120-130 r/min for 30 minutes, 3 parts by mass of photoinitiator (819) is weighed, 0.5 part by mass of flatting agent is added into the mixture, the mixture is continuously stirred at a speed of 120-130 r/min for 15 minutes, and static defoaming is carried out.
It should be noted that the formulation and manner of configuring the photo-curable mixture are not limited to the specific formulation and manner of configuration, and other formulations and configurations may be used under the precondition.
Optionally, the second preset ratio is: 15 parts by mass of 10-nanometer-particle-size metal oxide nanoparticles are dispersed in 51.9 parts by mass of ethyl acetate, 1-methoxy-2-propanol, methyl ethyl ketone, a xylene mixed solvent, 3 parts by mass of epoxy resin oligomer, 1210 parts by mass of epoxy resin oligomer, 68 parts by mass of phenolic resin ethylene glycol diglycidyl ether, 2.1 parts by mass of a toughening agent, 5 parts by mass of a curing agent 4,4' -Diamino Diphenyl Sulfone (DDS), and 5 parts by mass of an accelerator 2-methylimidazole (accounting for 0.1% of the epoxy resin).
The step of configuring the thermally curable mixture according to the second preset formulation comprises:
15 parts by mass of metal oxide nanoparticles with the particle size of 10 nanometers are weighed and dispersed in 51.9 parts by mass of mixed solvent of ethyl acetate, 1-methoxy-2-propanol, methyl ethyl ketone and xylene, and the mixture is subjected to ultrasonic dispersion for 15 minutes to form light blue clear liquid. 3 parts by mass of epoxy resin oligomer is added, the speed is 120r/min-130r/min, and the stirring time is 120 min, so that the epoxy resin oligomer is modified and coated on the surface of the nano particle. Then weighing 1210 parts by mass of epoxy resin oligomer, 68 parts by mass of phenolic resin ethylene glycol diglycidyl ether and 2.1 parts by mass of flexibilizer, continuously stirring and mixing for 60 minutes, then adding 5 parts by mass of curing agent 4,4' -diaminodiphenyl sulfone (DDS), and 5 parts by mass of accelerator 2-methylimidazole (accounting for 0.1% of epoxy resin) and other auxiliary agents, continuously stirring for 15 minutes, and standing for later use.
It should be noted that the formulation and manner of preparing the thermosetting mixture are not limited to the specific formulation and manner of preparing, and other formulations and configurations may be used under the precondition.
Optionally, the step of uniformly coating the anti-glare film material composition on a substrate to form an anti-glare film primary product includes:
setting the rotating speed of the spin coater to 300r/min;
the anti-glare film material composition was coated onto a 250 μm thick PET substrate to form an anti-glare film primary product.
At this time, the rotating speed of the spin coater is set at 300r/min, so that the coating uniformity and the thickness can be controlled in a reasonable range, and the influence of the substrate on the subsequent photo-curing and thermosetting effects can be reduced by coating the anti-glare film material composition on the PET substrate with the thickness of 250 micrometers.
Optionally, the first preset ratio is 1:8 or 1:20 or 1:8 or 1:10.
In the first case, the mixture A is cured by light: the mixture B was mixed at a ratio of 1:8, and the mixture was coated and cured as above to prepare an antiglare film.
In the second case, the mixture A is cured by light: the thermosetting mixture B was mixed in a ratio of 1:20. The anti-glare film is prepared by the same steps of coating and curing.
In the third case, the mixture A is cured by light: the thermosetting mixture B is mixed in a ratio of 1:8, and 2% of fluorocarbon resin LF710 is added to be stirred, dissolved and dispersed. The anti-glare film is prepared by the same steps of coating and curing.
In the fourth case, the average particle size of the metal oxide nanoparticles in the thermally curable mixture B is about 20nm. The photo-setting mixture A and the thermosetting mixture B are weighed and mixed into a glare-resistant film material composition in a ratio of 1:10. Coating and curing are carried out simultaneously, and the anti-glare film is prepared.
In the fifth case, the thermosetting mixture B is mixed in a ratio of 1:5, and stirred to obtain the anti-glare film material composition.
The invention also provides a manufacturing method of the anti-dazzle film die, which comprises the following steps:
aging the anti-glare film primary finished product manufactured by the manufacturing method of the anti-glare film to obtain an anti-glare film die;
carrying out UV transfer printing on the anti-dazzle film die to obtain an anti-dazzle structure film;
coating a UV glue solution on the transferred anti-glare structure film to realize UV curing;
and aging the anti-glare structure film to obtain the anti-glare film mold.
The following examples illustrate the application of anti-glare films:
1. preparing an anti-glare film die: step 1, taking an anti-dazzle film finished product prepared by the preparation method of the anti-dazzle film as a raw film, and preparing an anti-dazzle film die through ageing treatment; and 2, copying the anti-glare structure film through UV transfer printing. And 3, preparing a UV adhesive solution, coating the UV adhesive solution on the transferred anti-dazzle structural film, enabling the depth of the random microstructure to be shallow, and carrying out UV curing to obtain the anti-dazzle structural film, wherein the test haze is about 40%. And 4, aging the anti-dazzle membrane with the haze of about 40% again to prepare the anti-dazzle membrane die.
2. Anti-glare film application: agaf film preparation: the silica gel film is selected as a base material, and an anti-glare (AG) structure is duplicated through a UV transfer technology (dispensing-pressing-curing-separating) by using the prepared anti-glare film mold with the haze of 40%. Coating a layer of anti-fingerprint (AF) liquid on the surface of the AG structure film by using a spraying process, and baking at 120 ℃ for 30 minutes to obtain the AGAF film. The hydrophobic angle of the AGAF film is more than 110 degrees, and the wear resistance is good. The back film of the silica gel film is removed, and the anti-dazzle protective film can be directly attached to a high-pixel display screen (such as a mobile phone, a computer and the like) to be used as an anti-dazzle protective film.
Alternatively, the UV glue solution is an ethanol solution of 2% UV transfer glue. The foregoing is merely to illustrate an alternative real-time scheme, and in practical application, the structural depth of the UV transfer mold may be further finely adjusted by applying a diluted UV glue solution;
for example: 1. by changing the coating pressure, the thickness of the coating layer is changed, so that the structure depth is changed;
2. by varying the solution concentration, for example, after dilution, the thickness of the coating layer is reduced, resulting in a shallower depth of structure;
3. by changing the material proportion of the solution, the solution is more viscous, and the generated structural morphology can be changed.
In the above examples, AG structured molds of different haze (20% -80%) were prepared by fine-tuning the structural dimensions of random micro-wrinkles by AG structured mold preparation process using the prepared antiglare film primary product as a master. Then, a method for mass-producing an anti-glare film for a high pixel resolution screen using UV shape transfer can be used, while obtaining anti-glare properties and high contrast and preventing flash points.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.

Claims (4)

1.A method for producing an antiglare film, comprising:
determining a first preset proportion of the photo-curing mixture and a second preset proportion of the thermosetting mixture according to the proportion of the photo-curing mixture of the anti-glare film and the thermosetting mixture of the anti-glare film and the component content;
the step of configuring the photocurable mixture according to the first preset proportion comprises the following steps:
15 parts by mass of polyester acrylate prepolymer, 5 parts by mass of epoxy acrylate prepolymer, 10 parts by mass of dipentaerythritol hexaacrylate, 35 parts by mass of trimethylolpropane triacrylate and 31.5 parts by mass of tripropylene glycol diacrylate are weighed and mixed, the stirring time is 30 minutes, 3 parts by mass of photoinitiator (819) is weighed, 0.5 part by mass of flatting agent is added into the mixture, the stirring time is 15 minutes, and the mixture is static defoaming;
the step of configuring the thermally curable mixture according to the second preset formulation comprises:
15 parts by mass of metal oxide nano particles with the particle size of 10 nanometers are weighed and dispersed in 51.9 parts by mass of mixed solvent of ethyl acetate, 1-methoxy-2-propanol, methyl ethyl ketone and xylene, and the mixture is subjected to ultrasonic dispersion for 15 minutes to form light blue clear liquid; 3 parts by mass of epoxy resin oligomer is added, the speed is 120r/min-130r/min, and the stirring time is 120 min, so that the epoxy resin oligomer is modified and coated on the surface of the nano particle; weighing 1210 parts by mass of epoxy resin oligomer, 68 parts by mass of phenolic resin ethylene glycol diglycidyl ether, 2.1 parts by mass of flexibilizer, continuously stirring and mixing for 60 minutes, then adding 5 parts by mass of curing agent 4,4' -diaminodiphenyl sulfone (DDS), 0.1% accelerator 2-methylimidazole and 5 parts by mass of other auxiliary agents, continuously stirring for 15 minutes, and standing for later use;
mixing the photo-curing mixture and the heat-curing mixture according to the proportion to obtain an anti-dazzle film material composition, wherein the proportion is 1:8 or 1:20 or 1:10;
uniformly coating the anti-glare film material composition on a substrate to form an anti-glare film primary product;
introducing a first gas to thermally cure the anti-glare film primary finished product at a first temperature within a first preset time length;
performing light curing on the anti-glare film primary finished product after heat curing for a second preset time length at a first preset light intensity;
and (3) placing the thermally cured and photo-cured anti-glare film primary finished product into plasma for a third preset time length to obtain an anti-glare film finished product.
2. The method for manufacturing an antiglare film according to claim 1, wherein the step of placing the thermally cured and photo-cured antiglare film preform into a plasma for a third predetermined length of time to obtain an antiglare film preform further comprises:
coating an anti-fingerprint liquid (AF) on the surface of the anti-dazzle film finished product to prepare an AGAF film; or alternatively, the first and second heat exchangers may be,
coating a coating with low refractive index and high refractive index on the lamination of the anti-dazzle film finished product, and then coating AF liquid to prepare the AGARAF film.
3. The manufacturing method of the anti-dazzle film die is characterized by comprising the following steps of:
aging the anti-glare film primary product manufactured by the manufacturing method of the anti-glare film according to any one of claims 1-2 to obtain an anti-glare film mold;
carrying out UV transfer printing on the anti-dazzle film die to obtain an anti-dazzle structure film;
coating a UV glue solution on the transferred anti-glare structure film to realize UV curing;
and aging the anti-glare structure film to obtain the anti-glare film mold.
4. An antiglare film produced by the method for producing an antiglare film according to any one of claims 1 to 2.
CN202210383493.6A 2022-04-12 2022-04-12 Anti-glare film, manufacturing method and mold manufacturing method Active CN114895386B (en)

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