CN112480454A - Anti-dazzle hardening film for liquid crystal display - Google Patents
Anti-dazzle hardening film for liquid crystal display Download PDFInfo
- Publication number
- CN112480454A CN112480454A CN202011282142.3A CN202011282142A CN112480454A CN 112480454 A CN112480454 A CN 112480454A CN 202011282142 A CN202011282142 A CN 202011282142A CN 112480454 A CN112480454 A CN 112480454A
- Authority
- CN
- China
- Prior art keywords
- parts
- film
- weight
- liquid crystal
- antiglare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating 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
- G09F9/35—Indicating 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 being liquid crystals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
- C08J2301/12—Cellulose acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Theoretical Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Optical Elements Other Than Lenses (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of thin films, in particular to an anti-dazzle hardening film for liquid crystal display, which comprises the following substances in parts by weight: 15-45 parts of polyurethane acrylate resin; 5-30 parts of reactive diluent; 0.01 to 5 portions of flatting agent; 3-20 parts of micron-sized organic particles; 3-10 parts of a photoinitiator; 5-35 parts of modified nano silicon dioxide; 30-60 parts of organic solvent. Which has low haze and improved light transmittance and abrasion resistance without losing display characteristics such as high definition and anti-glare properties.
Description
Technical Field
The invention relates to the technical field of thin films, in particular to an anti-dazzle hardening film for liquid crystal display.
Background
Liquid crystal display products are developed towards optical requirements such as high contrast, wide viewing angle, high definition, and the like. However, since the general image display has an external light source in most of its usage environments, the light reflected from the display surface will cause a glare effect, which affects the visual experience of the viewer. The outer surface of the display may require some treatment to reduce the adverse effects of glare on viewing by the human eye. Therefore, the outermost protective film of the lcd needs to have low haze, high transmittance, anti-glare property, and anti-friction property. Particularly, in the case where the size demand is becoming larger and the thickness is becoming thinner in the current trend of liquid crystal televisions, the demand for the protective film is becoming higher.
The liquid crystal display is generally coated with an anti-glare film, and the degree of light scattering is controlled by controlling the internal diffusion or the external diffusion of light irradiated to the anti-glare film to suppress glare. The internal haze, i.e. internal diffusion, is to control the degree of light scattering by using various materials with different refractive indexes in the anti-dazzle film according to the conditions of refractive index difference, content proportion and size type; the external haze, i.e., external diffusion, controls the degree of light scattering by the shape, size, and the like of the surface of the optical film. The anti-glare effect mainly prevents the damage of external light to the reflection of human eyes, and then plays a role in diffusion scattering in the film to solve the trailing phenomenon of the liquid crystal picture and improve the definition of the liquid crystal picture.
In the prior art, various high-definition anti-glare films have been proposed, for example, a curable resin containing various micro-and nano-particles is coated on a transparent film material and cured to cause the micro-particles to generate a coagulation phenomenon and protrude out of the film surface, but the particles are easy to settle in the coating process, the particles are difficult to protrude out of the surface, the film surface is bright and the anti-glare effect is insufficient, meanwhile, the problem of poor wear resistance is caused due to poor adhesion with the coating layer because more particles are added, and the particles on the film surface are easy to fall off to form a powder falling phenomenon after a wear resistance test is carried out. Another mode of antiglare film is a film in which a co-continuous phase separation structure is formed on the surface of a cured film by utilizing compatibility between two to three kinds of resins, and this structure has very excellent antiglare properties, but has disadvantages of excessively high haze and poor adhesion of the surface resin due to poor resin compatibility. Therefore, it is generally difficult to meet the requirements of the image display, especially the requirements of the outermost protective film of the display.
Disclosure of Invention
The present application provides an antiglare hardened film for liquid crystal display, which has low haze and improved light transmittance and rubbing resistance without losing display characteristics such as high definition and antiglare property.
In order to achieve the technical purpose, the technical scheme adopted by the application is that the anti-dazzle hardening film for the liquid crystal display comprises the following substances in parts by weight:
15-45 parts of polyurethane acrylate resin
5 to 30 portions of reactive diluent
0.01 to 5 portions of flatting agent
5 to 20 portions of micron-sized organic particles
3 to 10 portions of photoinitiator
5 to 35 portions of modified nano silicon dioxide
30-70 parts of organic solvent.
As an improved technical scheme of the application, the micron-sized organic particles are monodisperse particles with a particle size DOrganic compoundsIs between 1 and 10 mu m.
As an improved technical scheme of the application, the modified nano-silica has a particle size of 10 nm-500 nm and has the following structure:
wherein: the structure of R is toluene, diphenylmethane, xylylene, hexamethylene, isophorone or dicyclohexylmethane; m represents silica particles; n is between 2 and 5.
As an improved technical scheme of the application, the modified nano-silica is modified nano-silica grafted with urethane acrylate and is obtained by modifying isocyanate and hydroxyl acrylate.
As an improved technical scheme of the application, the thickness H of the coating layer of the anti-dazzle hardened film is 2.5-25 mu m and 2DOrganic compounds<H。
As an improved technical scheme of the application, the polyurethane acrylate resin is one of aliphatic polyurethane acrylate resin or aromatic polyurethane acrylate resin, and the functionality number of the acrylate resin is 5-9.
As an improved technical scheme of the application, the haze of the anti-dazzle hardening film is 0.5-10%, wherein the internal haze ratio is 30-70%, and the light transmittance is 92-96%.
As a modified technical scheme of the application, the transparent support of the anti-dazzle hardening film is a cellulose triacetate film, and the thickness of the transparent support is 25 nm-100 nm.
Compared with the prior art, the invention has the following advantages:
1. the product is characterized in that large particles are completely embedded in the coating to control the light scattering degree, so that the trailing phenomenon of a liquid crystal picture is solved, and the definition of the liquid crystal picture is improved. The nano particles protrude on the surface of the film to play a role of anti-glare.
2. Compared with common high-precision polarizer hardened films, the product has lower haze value, better anti-dazzle property and excellent light transmittance, can achieve high precision due to low haze value, can prevent white blurring from an inclined direction, and is beneficial to improving the blackness and definition of a display.
3. Compared with common high-precision polarizer hardened films, the product can obviously improve the wear resistance of the films and can be used for the outermost protective film of the liquid crystal display. Generally, the micro-particles and the nano-particles are used in cooperation in the high-precision polarizer hardened film, but after the particles protrude out of the surface of the film, particularly the nano-particles have the problem of adhesion between the particles and a coating, the wear-resisting property is obviously poor, and the wear-resisting area is obviously similar to the powder falling situation. The product is modified and optimized on the surface of the nano particles, and isocyanate and acrylic hydroxyl ester are grafted on the nano particles, so that the nano particles can perform photocuring effect with the coating during curing, the adhesion between the nano particles and the coating is improved, and the wear resistance of the hardened film is improved.
4. Through modification treatment of the nano silicon dioxide, because the surface of the nano silicon dioxide is grafted with the polyurethane acrylate, the nano silicon dioxide is not easy to agglomerate in a formula solution, the dispersibility is good, and a nano particle dispersing agent is not required to be additionally added, so that the appearance of a coating is improved, and the generation of crystal points is reduced.
In conclusion, the technical scheme of the application effectively solves the problems of particle shedding, high haze and the like in the prior art. An antiglare cured film having a low haze and improved light transmittance, clarity, and rubbing resistance is obtained without losing display characteristics such as high definition and antiglare property.
Drawings
FIG. 1 is a schematic cross-sectional view of the present invention.
In the drawings, the reference numerals denote, 1: a transparent support; 2: an anti-glare hardened film; 3: micron-sized organic particles; 4: modified nano-silica particles.
Detailed Description
An antiglare cured film for liquid crystal display, the antiglare cured film having a coating layer with a thickness H of 2.5 to 25 μm and a 2DOrganic compounds<H. Ensuring that the film has a structure shown in figure 1, namely, a transparent support 1 (a cellulose triacetate film) is used as a support, an anti-dazzle hardened film 2 coating is coated on the surface, and micron-sized organic particles in the coating are dispersed in the coatingIn the layer, the modified nano-silica particles are combined with organic matters in the coating due to the organic part, so that the viscosity of the silica particles and the coating is ensured.
The anti-dazzle hardening film comprises the following substances in parts by weight:
15-45 parts of polyurethane acrylate resin
5 to 30 portions of reactive diluent
0.01 to 5 portions of flatting agent
3 to 20 portions of micron-sized organic particles
3 to 10 portions of photoinitiator
5 to 35 portions of modified nano silicon dioxide
30-70 parts of organic solvent.
Wherein the micron-sized organic particles are monodisperse particles, and the particle size D is between 1 and 10 mu m.
The particle size of the modified nano silicon dioxide is 10 nm-500 nm, and the modified nano silicon dioxide has the following structure:
wherein: the structure of R is toluene, diphenylmethane, xylylene, hexamethylene, isophorone or dicyclohexylmethane; m represents silica particles; n is between 2 and 5. The modified nano silicon dioxide is obtained by modifying isocyanate and hydroxyl acrylate, and the reaction principle is as follows: when the polyurethane acrylate is synthesized, isocyanate can react with alcohol firstly and then react with acrylic hydroxyl ester; the surface of the nano silicon dioxide contains hydroxyl because of the problems of the preparation process, so that the modified nano silicon dioxide grafted with the polyurethane acrylate can be obtained by utilizing the hydroxyl to react with isocyanate and hydroxyl firstly and then react with the added acrylic hydroxyl ester in the process of modifying the nano silicon dioxide.
The polyurethane acrylate resin is one of aliphatic polyurethane acrylate resin or aromatic polyurethane acrylate resin, and the functionality of the acrylate resin is 5-9.
The haze of the anti-dazzle hardening film is 0.5-10%, wherein the internal haze accounts for 30-70%, and the light transmittance is 92-96%.
The transparent support body of the anti-dazzle hardening film is a cellulose triacetate film, and the thickness of the transparent support body is 25 nm-100 nm.
An example in detail:
the modified nanosilica in this example was prepared by placing 20g of nanosilica into 300ml of a mixed solvent of ethyl acetate and butanone (ethyl acetate: butanone 4:6) and performing ultrasonic dispersion in an ice-water bath for about 1 hour. The solution containing the nanoparticles was then transferred to a heatable water bath and the temperature was slowly raised to 75 ℃. 1.81g of diphenylmethane diisocyanate (MDI), 2.04g of isophorone diisocyanate (IPDI) or 2.14g of dicyclohexylmethane diisocyanate (HMDI) was added to 100ml of the mixed solvent in the above ratio, and after stirring for about 30min, the solution was slowly added to the nanoparticle-containing solution and stirring was continued. This stirring was continued for 6h at a speed of 500rpm and at a temperature of 75 ℃ under N2Under protection. 1.2ml of trimethylolpropane diacrylate (TMPDA) was added to the mixed solution, and the solution was kept at N2Stirring is carried out for 8h at 75 ℃ under protection, and the stirring speed is reduced to 200 rpm. After cooling to room temperature, the mixed solution was centrifuged at 6000 rpm. Washing the precipitate with the mixed solvent for several times, drying in a 55 deg.C oven to obtain 3 kinds of modified nanometer SiO2. MDI-added2-1, IPDI-added and marked as SiO2-2, HMDI-added and marked as SiO2-3. Wherein MDI, IPDI and HMDI are preferably Sigma-aldrich, nanometer SiO2Preferably, the material comprises Degussa A200, A380 or T600, Nanjing Tianxing New Material Co., Ltd, TSP-H10 or TSD-L20N.
Of course, any technical means in the prior art can be adopted to obtain the modified nano-silica with the following structure:
wherein: the structure of R is toluene, diphenylmethane, xylylene, hexamethylene, isophorone or dicyclohexylmethane; m represents silica particles; n is between 2 and 5.
The modified nano silicon dioxide is 5-35 parts by weight, preferably 5-30 parts by weight, and more preferably 5-25 parts by weight.
In the invention, the polyurethane acrylate resin is aromatic or aliphatic polyurethane acrylate with the functionality of 5-9; the weight portion of the polyurethane acrylate is 15-45 portions, preferably 20-40 portions, and more preferably 25-35 portions. Specifically, 6112-100NT, 6115J-80 from Changxing corporation; agisyn530 by Dismann; 776 chemical double bond chemical engineering; HP6919, CR90843 of a new material of Haohui; chemoattractant HN-1201.
In the present invention, the reactive diluent preferably comprises an acrylate diluent monomer, more preferably comprises one or more of a diol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, differentially alkoxylated trimethylolpropane triacrylate, a (meth) acrylate reactive diluent containing a methoxy end group; the weight part of the diluent monomer is 5-30 parts, preferably 5-20 parts, and more preferably 5-15 parts. Specifically, in the examples of the present invention, 7100, TPGPA DE0 or EB1160 monomers available from cyante corporation, SR9008, SR9012, CN386 monomers available from sandoma corporation, LR8956 monomers available from basf corporation may be used.
In the invention, the leveling agent preferably comprises one or more of non-reactive polyether organic silicon, reactive polyether modified organic silicon or reactive polyester modified organic silicon, acrylate leveling agent, fluorine modified acrylate copolymer, sulfonate fluorine leveling agent and carboxylate fluorocarbon surfactant; the weight part of the water-based flatting agent is 0.01-5 parts, preferably 0.05-4 parts, and more preferably 0.15-2.5 parts. Specifically, in the embodiment of the invention, BYK333, BYK3760, BYK3710 or BYK361 leveling agents of Bikk chemistry, TEGO Flow425, TEGO Glide440 or TEGO ZFS 460 of winning companies can be adopted.
In the invention, the micron-sized organic particles are preferably one or more of polymethyl methacrylate, polystyrene and a copolymer of methyl methacrylate and butyl acrylate; the weight part of the micron-sized organic particles is 3-20 parts, preferably 5-16 parts, and more preferably 5-12 parts. Specifically, in the embodiment of the present invention, Hengqi materials technology (Shanghai) company FE212A or HL602, and Guangzhou Si Bo chemical engineering Co., Ltd. XJY-8011, XJY-8015 or XJY-801E can be used.
In the present invention, the photoinitiator is a radical polymerization photoinitiator, such as: 1-hydroxycyclohexylphenylketone (184), 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone (907), benzoin dimethyl ether (651), 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide (TPO), 2-Isopropylthioxanthone (ITX), and the like. The photo-curing agent may be used alone, or 2 or more of them may be used in combination. The addition amount of the photoinitiator is 3 to 10 parts, preferably 5 to 10 parts, and more preferably 5 to 8 parts.
In order to ensure that the solvent is quickly and completely volatilized when the coating enters an oven for drying, the organic solvent is as follows: methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, butyl acetate, ethyl acetate, isopropanol, isobutanol, toluene or xylene or a mixture of two of the methyl isobutyl ketone, the cyclohexanone, the diisobutyl ketone, the butyl acetate, the ethyl acetate, the isopropanol, the isobutanol, the toluene or the xylene. The addition amount of the organic solvent is 30 to 70 parts.
The coating method is not specifically limited in the present invention as long as the coating layer can be formed, and the coating layer can be formed using conventional coating methods including a bar coating method, a blade coating method, a gravure coating method, a roll coating method, a slit coating method, and a Mayer bar coating method. The bar coating method and the gravure coating method are preferable.
The present invention will be specifically described below with reference to specific examples, but the present invention is not limited thereto.
Example 1
15 parts by weight of urethane acrylate (Changxing Co. 6115J-80) was added to 68.85 parts by weight of a solvent (13.77 parts by weight of methyl isobutyl ketone, 41.31 parts by weight of ethyl acetate and 13.77 parts by weight of isopropyl alcohol), dissolved and stirred uniformly. 0.15 part by weight of polyether organic silicon flatting agent (BYK-3710, Saibei), 5 parts by weight of tertiary amine acrylate (7100, Cyanote) and 3 parts by weight of photoinitiator 1-hydroxycyclohexyl phenyl ketone are added and stirred uniformly. Finally, 3 parts by weight of micron-sized organic particles (Yongqi materials HL602, particle size 3 μm) and 5 parts by weight of nano-sized modified silica particles (Degussa A200, particle size 10nm, SiO 2) were added2-1) stirring and dispersing at high speed for 20min, wherein the stirring speed is 1200 r/min.
Coating the coating solution on one surface of optical grade cellulose triacetate film (TAC film) with thickness of 80 μm with a wire bar coater, drying in oven at 60 deg.C for 3min, and curing the dried coating by ultraviolet irradiation with dose of 250mJ/cm2And obtaining the prepared hardened film. The haze transmittance, the wear resistance and the internal haze ratio of the alloy are tested.
Example 2
25 parts by weight of urethane acrylate (Changxing Co. 6115J-80) was added to 68.85 parts by weight of a solvent (13.77 parts by weight of methyl isobutyl ketone, 41.31 parts by weight of ethyl acetate and 13.77 parts by weight of isopropyl alcohol), dissolved and stirred uniformly. 0.15 part by weight of polyether organic silicon flatting agent (BYK-3710 of Pico company), 5 parts by weight of tertiary amine acrylate (7100 of Cyanote company) and 3 parts by weight of photoinitiator 1-hydroxycyclohexyl phenyl ketone are added and stirred evenly. Finally, 3 parts by weight of micron-sized organic particles (Yongqi materials HL602, particle size 3 μm) and 5 parts by weight of nano-sized modified silica particles (Degussa A200, particle size 10nm, SiO 2) were added2-2) stirring and dispersing at high speed for 20min, wherein the stirring speed is 1200 r/min.
Coating the coating solution on one surface of optical grade cellulose triacetate film (TAC film) with thickness of 80 μm with a wire bar coater, drying in oven at 60 deg.C for 3min, and curing the dried coating by ultraviolet irradiation with dose of 250mJ/cm2And obtaining the prepared hardened film. The haze transmittance, the wear resistance and the internal haze ratio of the alloy are tested.
Example 3
25 parts by weight of urethane acrylate (Changxing Co. 6115J-80) was added to 68.85 parts by weight of a solvent (13.77 parts by weight of methyl isobutyl ketone, 41.31 parts by weight of ethyl acetate and 13.77 parts by weight of isopropyl alcohol), dissolved and stirred uniformly. 0.15 part by weight of polyether organic silicon flatting agent (BYK-3710 of Pico company), 5 parts by weight of tertiary amine acrylate (7100 of Cyanote company) and 3 parts by weight of photoinitiator 1-hydroxycyclohexyl phenyl ketone are added and stirred evenly. Finally, 3 parts by weight of micron-sized organic particles (Yongqi materials HL602, particle size 3 μm) and 5 parts by weight of nano-sized modified silica particles (Degussa A200, particle size 10nm, SiO 2) were added2-3) stirring and dispersing at high speed for 20min, wherein the stirring speed is 1200 r/min.
Coating the coating solution on one surface of optical grade cellulose triacetate film (TAC film) with thickness of 80 μm with a wire bar coater, drying in oven at 60 deg.C for 3min, and curing the dried coating by ultraviolet irradiation with dose of 250mJ/cm2And obtaining the prepared hardened film. The haze transmittance, the wear resistance and the internal haze ratio of the alloy are tested.
Example 4
45 parts by weight of urethane acrylate (Dismantan Agisyn530) was added to 15.5 parts by weight of a solvent (3.1 parts by weight of methyl isobutyl ketone, 9.3 parts by weight of ethyl acetate and 3.1 parts by weight of isopropyl alcohol), dissolved and stirred uniformly. 2.5 parts by weight of a polysiloxane-polyether copolymer leveling agent (TEGO Glide440, Digao Co.), 10 parts by weight of acrylate (SR 9012, Saedoma Co.) and 7 parts by weight of a photoinitiator 1-hydroxycyclohexylphenyl ketone are added and stirred uniformly. Finally, 12 weight parts of micron-sized organic particles (XJY-8015, 1 μm, Sibo chemical Co.) and 15 weight parts of nano-sized modified silica particles (Degussa T600, particle size 500nm, SiO 2) are added2-3) stirring and dispersing at high speed for 20min, wherein the stirring speed is 1200 r/min.
Coating the coating solution on one surface of optical grade cellulose triacetate film (TAC film) with thickness of 80 μm with a wire bar coater, drying in oven at 60 deg.C for 3min, and curing the dried coating by ultraviolet irradiation with dose of 250mJ/cm2And obtaining the prepared hardened film. The haze transmittance, the wear resistance and the internal haze ratio of the alloy are tested.
Example 5
28 parts by weight of urethane acrylate (Tadelk HN-1201) was added to 23.8 parts by weight of a solvent (4.76 parts by weight of methyl isobutyl ketone, 14.28 parts by weight of ethyl acetate and 4.76 parts by weight of isopropyl alcohol), dissolved and stirred uniformly. 1.2 parts by weight of polyacrylate leveling agent (TEGO ZFS 460 from Digao), 10 parts by weight of tertiary amine acrylate (LR 8956 from Pasteur) and 7 parts by weight of photoinitiator 1-hydroxycyclohexylphenylketone are added and stirred uniformly. Finally adding 20 parts by weight of micron-sized particlesOrganic particles (XJY-801E, Sibo chemical Co., Ltd., particle size 10 μm) and 10 parts by weight of nano-modified silica particles (Degussa A200, particle size 10nm, SiO 2)2-3) stirring and dispersing at high speed for 20min, wherein the stirring speed is 1200 r/min.
Coating the coating solution on one surface of optical grade cellulose triacetate film (TAC film) with thickness of 80 μm with a wire bar coater, drying in oven at 60 deg.C for 3min, and curing the dried coating by ultraviolet irradiation with dose of 250mJ/cm2And obtaining the prepared hardened film. The haze transmittance, the wear resistance and the internal haze ratio of the alloy are tested.
Example 6
28 parts by weight of urethane acrylate (776, double bond chemical company) was added to 13.2 parts by weight of a solvent (2.64 parts by weight of methyl isobutyl ketone, 7.92 parts by weight of ethyl acetate and 2.64 parts by weight of isopropyl alcohol), dissolved and stirred uniformly. 0.8 part by weight of a polyether modified dimethyl polysiloxane copolymer leveling agent (BYK-333, Pico), 9 parts by weight of tertiary amine acrylate (TPGPA DE0, Cyanote) and 7 parts by weight of a photoinitiator 1-hydroxycyclohexyl phenyl ketone are added and stirred uniformly. Finally, 7 parts by weight of micro-sized organic particles (Yongqi materials FE212A, particle size 2 μm) and 20 parts by weight of nano-sized modified silica particles (Degussa A200, particle size 10nm, SiO 2) were added2-3) stirring and dispersing at high speed for 20min, wherein the stirring speed is 1200 r/min.
Coating the coating solution on one surface of optical grade cellulose triacetate film (TAC film) with thickness of 80 μm with a wire bar coater, drying in oven at 60 deg.C for 3min, and curing the dried coating by ultraviolet irradiation with dose of 250mJ/cm2To obtain a prepared hard materialAnd (5) film formation. The haze transmittance, the wear resistance and the internal haze ratio of the alloy are tested.
Example 7
28 parts by weight of urethane acrylate (Haohui New materials, CR90843) was added to 26 parts by weight of a solvent (5.2 parts by weight of methyl isobutyl ketone, 12 parts by weight of ethyl acetate and 5.2 parts by weight of isopropyl alcohol), and the mixture was dissolved and stirred uniformly. 1 part by weight of an acrylate copolymer leveling agent (BYK-361, Bick company), 8 parts by weight of a tertiary amine acrylate (EB 1160, Cyanote company) and 7 parts by weight of a photoinitiator 1-hydroxycyclohexyl phenyl ketone were further added and stirred uniformly. Finally, 10 weight parts of micron-sized organic particles (XJY-8011, 2 μm, Sibo chemical company) and 20 weight parts of nano-sized modified silica particles (Degussa A200, particle size 10nm, SiO 2) are added2-3) stirring and dispersing at high speed for 20min, wherein the stirring speed is 1200 r/min.
Coating the coating solution on one surface of optical grade cellulose triacetate film (TAC film) with thickness of 80 μm with a wire bar coater, drying in oven at 60 deg.C for 3min, and curing the dried coating by ultraviolet irradiation with dose of 250mJ/cm2And obtaining the prepared hardened film. The haze transmittance, the wear resistance and the internal haze ratio of the alloy are tested.
Comparative example 1
15 parts by weight of urethane acrylate (Changxing Co. 6115J-80) was added to 68.85 parts by weight of a solvent (13.77 parts by weight of methyl isobutyl ketone, 41.31 parts by weight of ethyl acetate and 13.77 parts by weight of isopropyl alcohol), dissolved and stirred uniformly. 0.15 part by weight of polyether organic silicon flatting agent (BYK-3710 of Pico company), 5 parts by weight of tertiary amine acrylate (7100 of Cyanote company) and 3 parts by weight of photoinitiator 1-hydroxycyclohexyl phenyl ketone are added and stirred evenly. Finally, 3 parts by weight of micron-sized organic particles (Hedgey materials, HL602, particle size of 3 μm) and 5 parts by weight of nano-sized silica particles (Degussa A200, particle size of 10nm) are added to be stirred and dispersed at a high speed of 1200r/min for 20 min.
Coating the coating solution on one surface of optical grade cellulose triacetate film (TAC film) with thickness of 80 μm with a wire bar coater, drying in oven at 60 deg.C for 3min, and curing the dried coating by ultraviolet irradiation with dose of 250mJ/cm2And obtaining the prepared hardened film. The haze transmittance, the wear resistance and the internal haze ratio of the alloy are tested.
Comparative example 2
45 parts by weight of urethane acrylate (Dismantan Agisyn530) was added to 15.5 parts by weight of a solvent (3.1 parts by weight of methyl isobutyl ketone, 9.3 parts by weight of ethyl acetate and 3.1 parts by weight of isopropyl alcohol), dissolved and stirred uniformly. 2.5 parts by weight of a polysiloxane-polyether copolymer leveling agent (TEGO Glide440, Digao Co.), 10 parts by weight of acrylate (SR 9012, Saedoma Co.) and 7 parts by weight of a photoinitiator 1-hydroxycyclohexylphenyl ketone are added and stirred uniformly. Finally, 12 parts by weight of micron-sized organic particles (XJY-8015, 1 μm, from Sibo chemical company) and 15 parts by weight of nano-sized modified silica particles (Degussa T600, particle size 500nm) are added to be stirred and dispersed at a high speed for 20min, and the stirring speed is 1200 r/min.
The coating liquid was applied to one surface of an optical grade cellulose triacetate film (TAC film) having a thickness of 80 μm by a wire bar coaterDrying in oven at 60 deg.C for 3min, and curing the dried coating by ultraviolet irradiation with dose of 250mJ/cm2And obtaining the prepared hardened film. The haze transmittance, the wear resistance and the internal haze ratio of the alloy are tested.
Comparative example 3
28 parts by weight of urethane acrylate (Haohui New materials, CR90843) was added to 26 parts by weight of a solvent (5.2 parts by weight of methyl isobutyl ketone, 12 parts by weight of ethyl acetate and 5.2 parts by weight of isopropyl alcohol), and the mixture was dissolved and stirred uniformly. 1 part by weight of an acrylate copolymer leveling agent (BYK-361, Bick company), 8 parts by weight of a tertiary amine acrylate (EB 1160, Cyanote company) and 7 parts by weight of a photoinitiator 1-hydroxycyclohexyl phenyl ketone were further added and stirred uniformly. Finally, 10 weight parts of micron-sized organic particles (XJY-8011, 2 μm, Sibo chemical company) and 20 weight parts of nano-sized modified silica particles (Degussa A200, particle size 10nm) are added to be stirred and dispersed at high speed for 20min, and the stirring speed is 1200 r/min.
Coating the coating solution on one surface of optical grade cellulose triacetate film (TAC film) with thickness of 80 μm with a wire bar coater, drying in oven at 60 deg.C for 3min, and curing the dried coating by ultraviolet irradiation with dose of 250mJ/cm2And obtaining the prepared hardened film. The haze transmittance, the wear resistance and the internal haze ratio of the alloy are tested.
Compared with the examples 1-3, the sample appearance is obviously poorer without modified nano silicon dioxide, the agglomeration phenomenon of the nano particles is obvious, and the full-width large crystal point exists. The haze is higher, the light transmittance is lower, and the high-fineness effect is not achieved. Nor the good clarity of the modified nanoparticles across the sample. The abrasion resistance is tested, and the powder falling phenomenon of the comparative example is obvious.
Comparative example 2 compared with example 4, even if the resin amount was increased and the coating thickness was increased, the abrasion resistance of the sample piece could not be improved, there was a "dusting phenomenon" and the sample piece had poor clarity and had no high fineness effect.
Compared with the embodiments 5-7, the comparative example 3 has better definition of the sample wafer and has high fine effect. Even though the examples added more organic particles or modified nanoparticles, the properties of the samples of the examples, such as haze transmittance and abrasion resistance, were better than the comparative examples.
The test methods of the properties are as follows (the test results are shown in table 1):
(1) haze light transmittance test
The haze transmittance was measured using a haze meter (Nippon Denshoku Co., Ltd.; model: NDH 2000N).
(2) Scratch resistance of the coating
The scratch resistance of the antiglare layer was measured by the method specified in HG/T4303, the load was 500g, and the results were recorded as follows:
no scratch at all, recorded as "∘";
1-10 scratches, recorded as "Δ";
greater than 10 scratches, recorded as "x".
(3) Hardness of coated pencil
Film hardness tester (Haipanshi chemical machinery Co., Ltd., model: "BY") GB/T6739-1996 Standard advantage
The pencil hardness of the antiglare layer was measured by scratching the coating film with a pencil, and the weight was 500 g.
Table 1: test data table for each example and comparative example
Claims (8)
1. The anti-dazzle hardening film for the liquid crystal display is characterized by comprising the following substances in parts by weight:
15-45 parts of polyurethane acrylate resin
5 to 30 portions of reactive diluent
0.01 to 5 portions of flatting agent
3 to 20 portions of micron-sized organic particles
3 to 10 portions of photoinitiator
5 to 35 portions of modified nano silicon dioxide
30-70 parts of organic solvent.
2. The antiglare hardened film for liquid crystal displays according to claim 1, wherein the micron-sized organic particles are monodisperse particles having a particle diameter DOrganic compoundsIs between 1 and 10 mu m.
3. The antiglare hardened film for liquid crystal displays according to claim 1, wherein the modified nanosilica has a particle size of 10nm to 500nm and the following structure:
wherein: the structure of R is toluene, diphenylmethane, xylylene, hexamethylene, isophorone or dicyclohexylmethane; m represents nano silicon dioxide particles; n is between 2 and 5.
4. The antiglare hardened film for liquid crystal displays according to claim 3, wherein the modified nanosilica is a modified nanosilica grafted with urethane acrylate and modified with isocyanate and hydroxy acrylate.
5. The antiglare hardened film for liquid crystal display according to claim 1, wherein the coating layer of the antiglare hardened film has a thickness H of 2.5 to 25 μm and a 2DOrganic compounds<H。
6. The antiglare cured film for liquid crystal display according to claim 1, wherein the urethane acrylate resin is one of an aliphatic urethane acrylate resin and an aromatic urethane acrylate resin, and a functionality of the acrylate resin is 5 to 9.
7. The antiglare hardened film for liquid crystal displays of claim 1, wherein the antiglare hardened film has a haze of 0.5% to 10%, an internal haze of 30% to 70%, and a light transmittance of 92% to 96%.
8. The cured antiglare film for liquid crystal displays according to claim 1, wherein the transparent support of the cured antiglare film is a cellulose triacetate film having a thickness of 25nm to 100 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011282142.3A CN112480454A (en) | 2020-11-17 | 2020-11-17 | Anti-dazzle hardening film for liquid crystal display |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011282142.3A CN112480454A (en) | 2020-11-17 | 2020-11-17 | Anti-dazzle hardening film for liquid crystal display |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112480454A true CN112480454A (en) | 2021-03-12 |
Family
ID=74931254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011282142.3A Pending CN112480454A (en) | 2020-11-17 | 2020-11-17 | Anti-dazzle hardening film for liquid crystal display |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112480454A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114384623A (en) * | 2022-02-16 | 2022-04-22 | Tcl华星光电技术有限公司 | Polaroid, display panel and display device |
| CN114805896A (en) * | 2022-05-18 | 2022-07-29 | 苏州诺菲纳米科技有限公司 | Anti-glare protective film and preparation method thereof |
| CN115340817A (en) * | 2022-09-15 | 2022-11-15 | 中国科学技术大学 | Hardening coating with wide temperature range and high damping performance and preparation method thereof |
| CN115491119A (en) * | 2022-11-22 | 2022-12-20 | 宁波惠之星新材料科技股份有限公司 | Anti-dazzle liquid, anti-dazzle film, preparation method of anti-dazzle film and polarizer |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530321A (en) * | 2015-01-30 | 2015-04-22 | 合肥工业大学 | Preparation method of nanoparticle-modified polyurethane acrylate copolymer resin microemulsion |
| CN105038575A (en) * | 2015-09-21 | 2015-11-11 | 张家港康得新光电材料有限公司 | Water-based anti-dazzle UV coating, hard coated film and preparation method of hard coated film |
| CN106811108A (en) * | 2016-12-22 | 2017-06-09 | 张家港康得新光电材料有限公司 | A kind of anti-flash-point coating of anti-dazzle and preparation method and application |
| CN107840982A (en) * | 2017-11-09 | 2018-03-27 | 合肥乐凯科技产业有限公司 | A kind of anti-dazzle optical hardening film of fine definition |
| CN108129978A (en) * | 2017-12-25 | 2018-06-08 | 同济大学 | The preparation method of the nano-silicon dioxide modified urethane acrylate ultraviolet-curing paint of high-content |
| CN108690208A (en) * | 2017-03-07 | 2018-10-23 | 宁波惠之星新材料科技有限公司 | A kind of cured film with high tenacity and high-wearing feature |
| CN110058337A (en) * | 2019-04-25 | 2019-07-26 | 汕头万顺包装材料股份有限公司 | A kind of high definition antiglare film |
| US20200040198A1 (en) * | 2018-08-02 | 2020-02-06 | Benq Materials Corporation | Hard coating layered optical film, polarizer comprising the same, and image display comprising the hard coating layered optical film and/or the polarizer comprising the same |
| CN111040617A (en) * | 2019-12-26 | 2020-04-21 | 合肥乐凯科技产业有限公司 | Anti-dazzle hardening film for polaroid |
-
2020
- 2020-11-17 CN CN202011282142.3A patent/CN112480454A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530321A (en) * | 2015-01-30 | 2015-04-22 | 合肥工业大学 | Preparation method of nanoparticle-modified polyurethane acrylate copolymer resin microemulsion |
| CN105038575A (en) * | 2015-09-21 | 2015-11-11 | 张家港康得新光电材料有限公司 | Water-based anti-dazzle UV coating, hard coated film and preparation method of hard coated film |
| CN106811108A (en) * | 2016-12-22 | 2017-06-09 | 张家港康得新光电材料有限公司 | A kind of anti-flash-point coating of anti-dazzle and preparation method and application |
| CN108690208A (en) * | 2017-03-07 | 2018-10-23 | 宁波惠之星新材料科技有限公司 | A kind of cured film with high tenacity and high-wearing feature |
| CN107840982A (en) * | 2017-11-09 | 2018-03-27 | 合肥乐凯科技产业有限公司 | A kind of anti-dazzle optical hardening film of fine definition |
| CN108129978A (en) * | 2017-12-25 | 2018-06-08 | 同济大学 | The preparation method of the nano-silicon dioxide modified urethane acrylate ultraviolet-curing paint of high-content |
| US20200040198A1 (en) * | 2018-08-02 | 2020-02-06 | Benq Materials Corporation | Hard coating layered optical film, polarizer comprising the same, and image display comprising the hard coating layered optical film and/or the polarizer comprising the same |
| CN110058337A (en) * | 2019-04-25 | 2019-07-26 | 汕头万顺包装材料股份有限公司 | A kind of high definition antiglare film |
| CN111040617A (en) * | 2019-12-26 | 2020-04-21 | 合肥乐凯科技产业有限公司 | Anti-dazzle hardening film for polaroid |
Non-Patent Citations (1)
| Title |
|---|
| 许雨晴等: "原位聚合法制备UV固化聚氨酯丙烯酸酯/纳米二氧化硅杂化材料及其性能研究", 《塑料工业》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114384623A (en) * | 2022-02-16 | 2022-04-22 | Tcl华星光电技术有限公司 | Polaroid, display panel and display device |
| CN114384623B (en) * | 2022-02-16 | 2023-01-24 | Tcl华星光电技术有限公司 | Polaroid, display panel and display device |
| CN114805896A (en) * | 2022-05-18 | 2022-07-29 | 苏州诺菲纳米科技有限公司 | Anti-glare protective film and preparation method thereof |
| CN114805896B (en) * | 2022-05-18 | 2023-09-12 | 苏州诺菲纳米科技有限公司 | Anti-dazzle protective film and preparation method thereof |
| CN115340817A (en) * | 2022-09-15 | 2022-11-15 | 中国科学技术大学 | Hardening coating with wide temperature range and high damping performance and preparation method thereof |
| CN115340817B (en) * | 2022-09-15 | 2023-10-20 | 中国科学技术大学 | Hardening coating with wide temperature range and high damping performance and preparation method thereof |
| CN115491119A (en) * | 2022-11-22 | 2022-12-20 | 宁波惠之星新材料科技股份有限公司 | Anti-dazzle liquid, anti-dazzle film, preparation method of anti-dazzle film and polarizer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112480454A (en) | Anti-dazzle hardening film for liquid crystal display | |
| CN101796146B (en) | Self-assembling antireflective coating comprising surface modified high refractive index nanoparticles | |
| KR102118904B1 (en) | Anti-relrection composition and optical film using thereof | |
| CN111040617B (en) | Anti-dazzle hardening film for polaroid | |
| US10338276B2 (en) | Antireflective film, polarizing plate, cover glass, image display device, and method of manufacturing antireflective film | |
| JP5345891B2 (en) | Anti-glare film and method for producing the same | |
| JP5598892B2 (en) | Laminated transparent film | |
| TWI498391B (en) | Coating solution for forming transparent coated film and substrate with the transparent coated film | |
| TW201311836A (en) | Composition for anti-reflective coating and anti-reflective coating film using the same | |
| TWI573821B (en) | Application liquid for forming transparent coating and substrate with transparent coating | |
| KR20090023359A (en) | Metal oxide composition, cured film and laminate | |
| TW201522546A (en) | Inorganic particle dispersion, inorganic particle containing composition, coating film, plastic substrate with coating film, display | |
| TWI776297B (en) | Anti-glare film and polarizer with the same | |
| CN110119004B (en) | Anti-dazzle film and polarizing plate with same | |
| JP2014525056A (en) | Anti-glare film exhibiting high contrast ratio and method for producing the same | |
| CN112540421A (en) | Anti-dazzle film and polarizing plate with same | |
| TWI738382B (en) | Anti-glare film and polarizer with the same | |
| TWI693734B (en) | Anti-glare film and polarizer with the same | |
| TW201927398A (en) | Inorganic microparticle dispersion, curable composition, and optical member | |
| CN117487226A (en) | Anti-aging fluorescent carbon quantum dot antibacterial functional film | |
| CN114213961B (en) | Ultraviolet-proof hardening film | |
| KR20090049519A (en) | Coating composition for antireflection and antireflection film prepared by using the same | |
| JP2008081649A (en) | Resin mixture composition curable by ionizing radiation and layered product using the same | |
| CN113583560B (en) | Hardened layer coating liquid and hardened film | |
| JP6547749B2 (en) | Zirconium oxide, zirconium oxide dispersion liquid, zirconium oxide-containing composition, coating film, and display device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210312 |
|
| RJ01 | Rejection of invention patent application after publication |