CN114479152A

CN114479152A - High-hardness anti-dazzle film

Info

Publication number: CN114479152A
Application number: CN202111656021.5A
Authority: CN
Inventors: 邹清清; 刘楷楷; 董红星
Original assignee: NINGBO HUGHSTAR ADVANCED MATERIAL TECHNOLOGY CO LTD
Current assignee: NINGBO HUGHSTAR ADVANCED MATERIAL TECHNOLOGY CO LTD
Priority date: 2021-12-30
Filing date: 2021-12-30
Publication date: 2022-05-13
Anticipated expiration: 2041-12-30
Also published as: CN114479152B

Abstract

The invention discloses a high-hardness anti-dazzle film, which comprises an anti-dazzle layer and a transparent base material, wherein the anti-dazzle layer and the transparent base material are laminated from top to bottom, the surface of the anti-dazzle layer is provided with a concave-convex shape, the anti-dazzle layer is formed by coating anti-dazzle coating on the transparent base material to form a coating and then curing the coating, the anti-dazzle coating is obtained by blending 15-45 parts by weight of adhesive resin, 5-20 parts by weight of inorganic nano particles, 9.5-67.8 parts by weight of solvent, 1-6 parts by weight of photoinitiator, 0.1-2 parts by weight of flatting agent, 0.1-3 parts by weight of dispersing agent and 0.1-2.5 parts by weight of anti-fingerprint auxiliary agent, the solid weight content of the anti-dazzle coating is 30-50%, and the coating amount after curing of the coating is 21g/m²‑45g/m²The curing process of the coating on the transparent substrate is as follows: firstly thermally curing for 30-180 s at 50-130 ℃, and then performing photo-curing by adopting ultraviolet irradiation with the energy of 100mJ/cm²The above; the advantages are high anti-glare property, high hardness and high wear resistance.

Description

High-hardness anti-dazzle film

Technical Field

The invention relates to an anti-dazzle film, in particular to a high-hardness anti-dazzle film.

Background

When an image display device such as a liquid crystal display, an electronic paper, a tablet computer, and an electronic touch display screen is used, an anti-glare optical film for preventing glare is generally disposed on an outer surface of the screen. The anti-glare optical film is obtained by forming an anti-glare layer having a surface with a concavo-convex shape on a transparent substrate, wherein the anti-glare layer scatters external light by the concavo-convex shape of the surface, thereby preventing the visibility of screen display contents from being reduced due to the reflection of the external light or the reflection of an external image, and realizing an anti-glare function. Since the anti-glare optical film is disposed on the outer surface of the screen, in order to reduce the degree of damage and ensure the service life of the anti-glare optical film, the anti-glare optical film is required to have high hardness and high wear resistance.

At present, various anti-glare films have appeared on the market, and these anti-glare films mainly have two formation principles, the first is to form an anti-glare layer by using resin (containing filler such as silica), and to form a concave-convex shape on the surface of the anti-glare layer by micron-sized particles such as silica; in the second method, a film having irregularities formed by transfer is laminated on a transparent base material, whereby a specific irregular shape is formed on the surface of the antiglare film. In short, the antiglare film realizes an antiglare function by forming a surface roughness on the surface of an antiglare layer and scattering light. Thus, the antiglare properties of these antiglare films are correlated with their surface roughness, and the higher the surface roughness of the antiglare films, the better the antiglare properties. However, the improvement of the surface roughness causes an increase in the haze value of the antiglare film, a whitening phenomenon of the antiglare film, and a decrease in the contrast of a displayed image, and also greatly decreases the surface hardness and abrasion resistance of the antiglare film.

Disclosure of Invention

The invention aims to provide a high-hardness anti-dazzle film which has high anti-dazzle property, high hardness and high wear resistance.

The technical scheme adopted by the invention for solving the technical problems is as follows: a high-hardness anti-dazzle film is composed of an anti-dazzle layer with concave-convex shape on its surface and a transparent substrate, which are laminated from top to bottom, and an anti-dazzle layer with concave-convex shape on its surface is coated by anti-dazzle paintAnd then curing the coating to form the anti-glare coating, wherein the anti-glare coating is obtained by blending 15-45 parts by weight of adhesive resin, 5-20 parts by weight of inorganic nano particles, 9.5-67.8 parts by weight of solvent, 1-6 parts by weight of photoinitiator, 0.1-2 parts by weight of flatting agent, 0.1-3 parts by weight of dispersing agent and 0.1-2.5 parts by weight of anti-fingerprint auxiliary agent, the solid content of the anti-glare coating is 30-50%, and the coating weight of the cured coating is 21g/m²-45 g/m²The curing process of the coating on the transparent substrate is as follows: firstly thermally curing for 30-180 s at 50-130 ℃, and then performing photo-curing by adopting ultraviolet irradiation with the energy of 100mJ/cm²The above.

The adhesive resin is formed by mixing 10-30 parts by weight of urethane acrylate with the functionality of more than 5 and the molecular weight of 1000-5000-.

The inorganic nanoparticles are preferably amphiphilic inorganic nanoparticles with modified surfaces, the particle size is 50nm-700nm, and the inorganic nanoparticles are one or more of aluminum oxide nanoparticles, silicon oxide nanoparticles, titanium oxide nanoparticles and zirconium oxide nanoparticles.

The solvent is any one of methanol, ethanol, isopropanol, n-butanol, tert-butanol, PGME, ethylene glycol, acetone, methyl isobutyl ketone, cyclohexanone, butanone, hexane, cyclohexane, benzene, toluene, xylene, diethyl ether and propylene glycol methyl ether, and preferably is methyl isobutyl ketone.

The photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl phenyl acetone (1173) and 2, 4, 6-trimethyl benzoyl-diphenyl phosphine oxide (TPO). The preferred weight part is 1 to 3 weight parts.

The leveling agent is at least one of a fluorine leveling agent, a silicone leveling agent and an acrylic leveling agent, and preferably the fluorine leveling agent. The leveling agent can effectively reduce the surface tension of the coating and has the effect of adjusting the agglomeration of inorganic nano particles in the coating liquid.

The dispersant is an acrylic high-molecular dispersant, is used for dispersing the inorganic nanoparticles and regulating the agglomeration of the inorganic nanoparticles, and is one or more of a chelate copolymer, a block copolymer or a blend copolymer.

The fingerprint-proof auxiliary agent is at least one of perfluoropolymer, fluorine-containing polymer or fluorocarbon modified polymer.

The thickness of the anti-dazzle layer with the surface having the concave-convex shape is 15-30 μm, and the thickness of the transparent base material is 23-250 μm, preferably 125-250 μm; the transparent substrate is one of PET, TAC, SRF, PI, TPU and COP transparent substrates, and preferably PET transparent substrates.

The coating weight of the coating after curing is preferably 25g/m²-35 g/m²The curing process is preferably as follows: heating at 50-130 deg.C for 30-180 s, and photocuring by ultraviolet irradiation with energy of 180mJ/cm²The above.

Compared with the prior art, the invention has the advantages that: the anti-glare coating is obtained by blending 15-45 parts by weight of adhesive resin, 5-20 parts by weight of inorganic nanoparticles, 9.5-67.8 parts by weight of solvent, 1-6 parts by weight of photoinitiator, 0.1-2 parts by weight of flatting agent, 0.1-3 parts by weight of dispersant and 0.1-2.5 parts by weight of anti-fingerprint additive. The amphiphilic nano particles are uniformly dispersed in the adhesive resin under the synergistic action of the dispersing agent, but the amphiphilic nano particles and other components in the anti-glare coating still have a certain polarity difference, and can gradually agglomerate and float on the surface of the anti-glare layer along with the volatilization of the solvent in the thermosetting process. The inventor finds that part of nano inorganic particles in the anti-glare coating can be agglomerated by adjusting the proportion of each component in the anti-glare coating and controlling the thermosetting condition so as to form the concave-convex shape on the surface of the anti-glare layer through a large number of experiments; the other part of the nano particles which are not close to agglomerate are filled in the coating layer to improve the rigidity in the anti-dazzle layer, thereby improving the hardness and the wear resistance of the anti-dazzle film, so that the invention utilizes the polarity difference between the amphiphilic inorganic nano particles and other materials in the anti-dazzle coating to make the inorganic nano particles have 'one object and two purposes': the agglomerated part forms an anti-dazzle layer, and the unagglomerated part improves the hardness and wear resistance of the anti-dazzle film, so that the high-hardness anti-dazzle film can achieve higher surface hardness and friction resistance effect while meeting the anti-dazzle function, and has excellent anti-fouling performance and other physical properties.

Drawings

FIG. 1 is a structural view of a high-hardness antiglare film of the present invention;

FIG. 2 is a surface microstructure of an entire unagglomerated sample of comparative example of the present invention;

FIG. 3 is a surface microstructure diagram of an entire agglomerated sample of comparative example two of the present invention;

FIG. 4 is a surface microstructure diagram of the first embodiment of the present invention.

Detailed Description

The invention is described in further detail below with reference to the accompanying examples.

The first embodiment is as follows: as shown in figure 1, the high-hardness anti-dazzle film comprises an anti-dazzle layer 2 with a concavo-convex shape on the surface and a transparent substrate 1 which are laminated from top to bottom, wherein the anti-dazzle layer 2 with the concavo-convex shape on the surface is formed by coating an anti-dazzle coating on the transparent substrate 1 to form a coating layer and then curing the coating layer, the anti-dazzle coating is formed by blending 39.5 parts by weight of adhesive resin, 15 parts by weight of inorganic nano particles, 46.5 parts by weight of solvent, 3 parts by weight of photoinitiator, 0.5 part by weight of flatting agent, 1 part by weight of dispersing agent and 1 part by weight of anti-fingerprint auxiliary agent, the solid weight content of the anti-dazzle coating is 40 percent, and the coating amount after curing the coating layer is 30g/m²The curing process comprises the following steps: drying in oven at 70 deg.C for 90s at a running speed of 10m/min, and photocuring with ultraviolet irradiation energy of 180mJ/cm²。

In this example, the adhesive resin is a mixture of 32 parts by weight of 6-functionality urethane acrylate (selected from Changxing chemical 6145-100) and 7.5 parts by weight of 3-functionality urethane acrylate (selected from Changxing 6130B-80), the inorganic nanoparticles are nano inorganic alumina with a modified surface, selected from Nanjing Tianxing new material TAD, the solvent is methyl isobutyl ketone, the photoinitiator is a mixture of 0.5 part by weight of TPO produced by BASF company and 2.5 parts by weight of Irgacure184, the leveling agent is selected from Pickering chemical 410, the dispersant is selected from Pickering chemical 2025, and the anti-fingerprint auxiliary agent is selected from DIC RS 75.

In this example, the thickness of the antiglare layer 2 having a concavo-convex shape was 15 μm, the thickness of the transparent base material 1 was 250 μm, and the material of the transparent base material 1 was PET.

Example two: this example is substantially the same as the first example except that 45 parts by weight of the adhesive resin was used in this example. Specifically a mixture of 36 parts by weight of a 6-functional urethane acrylate and 9 parts by weight of a 3-functional urethane acrylate, while hot setting conditions were 120 ℃ and drying was carried out for 30 seconds.

Example three: this example is substantially the same as the first example, except that in this example, the amount of the inorganic nanoparticles is 20 parts by weight.

Example four: this example is substantially the same as the first example except that in this example, the inorganic nanoparticles are 5 parts by weight, the thermosetting condition is 130 ℃, and the drying time is 30 s.

Example five: this example is substantially the same as example one except that in this example, the adhesive resin is 12 parts by weight of 6-functional urethane acrylate (selected from Changxing chemical 6145-100) and 3 parts by weight of 3-functional urethane acrylate (selected from Changxing 6130B-80), totaling 15 parts by weight, and the leveling agent is 1.2 parts by weight.

Example six: this example is essentially the same as example one except that in this example, the tackifying resin is 24 parts by weight of 6 functional urethane acrylate (selected from Changxing chemical 6145-100) and 6 parts by weight of 3 functional urethane acrylate (selected from Changxing 6130B-80), totaling 30 parts by weight, with 2 parts by weight of dispersant.

Example seven: this example is substantially the same as the first example, except that in this example, the curing process of the coating is as follows: drying at 130 deg.C for 90s in oven at running speed of 10m/min, and irradiating with cumulative light amount of 180mJ/cm²Ultraviolet rays of (1).

Example eight: the present embodiment is substantially the same as the first embodiment, except that in the present embodiment, the inorganic nanoparticles are nabume SD50 nano-silica.

Comparative example one: this comparative example is substantially the same as example one except that in this comparative example, the amount of the inorganic nanoparticles is 3 parts by mass.

Comparative example two: this comparative example is substantially the same as example one except that in this comparative example, the inorganic nanoparticles were 22 parts by mass and the leveling agent and the dispersant were each 0.05 parts.

Comparative example three: this comparative example is essentially the same as example one, except that in this comparative example, the curing process of the coating is: drying at 45 deg.C in oven at a running speed of 10m/min for 20s, and irradiating with a cumulative light amount of 180mJ/cm²Ultraviolet rays of (1).

Comparative example four: this comparative example is essentially the same as example one, except that in this comparative example, the curing process of the coating is: drying at 150 deg.C in oven at running speed of 10m/min for 240s, and irradiating with cumulative light amount of 180mJ/cm²Ultraviolet rays of (1).

The products of the above examples and comparative examples were subjected to test evaluations of the following items, and the test results are shown in table 1:

table 1: results of the tests of examples one-eight and comparative examples one-four

Haze value

Anti-glare property

Antifouling property

Hardness of

Wear resistance

Cracking property

Example one

○

8H

1000 times (one time)

○

Example two

○

7H

1000 times (one time)

○

EXAMPLE III

○

8H

600 times (one time)

○

Example four

○

7H

700 times

○

EXAMPLE five

○

8H

800 times

○

EXAMPLE six

○

8H

700 times

○

EXAMPLE seven

○

7H

700 times

○

Example eight

○

8H

1000 times (one time)

○

Comparative example 1

×

○

7H

1000 times (one-time)

○

Comparative example No. two

×

○

6H

300 times (twice)

○

Comparative example No. three

○

×

○

8H

500 times (times)

○

Comparative example No. four

○

5H

150 times of

○

In the above table, haze values: the haze value of the obtained high-hardness antiglare film was measured according to GB-T2410-2008 and evaluated according to the following criteria:

o: the haze value is 25 to 35 percent

X: haze value below 25%, or above 35%

Pencil hardness: the surface pencil hardness (in which the load is 500g) of the obtained high-hardness antiglare film was measured in accordance with GB-T6739-:

6H: the surface pencil hardness is 6H

7H: the surface pencil hardness is 7H

8H: the surface pencil hardness is 8H

Anti-dazzle type: the antiglare property of the obtained antiglare film was evaluated by attaching the antiglare film to a black acrylic plate and observing the degree of reflection of the coating layer against the background of an observer:

o: good anti-dazzle property (observer can not be clearly observed)

X: poor anti-dazzle (obviously seeing observer background)

Antifouling property: the surface water contact angle of the obtained high-hardness antiglare film was measured according to GBT 30693-:

o: the surface water contact angle is more than or equal to 105 °

X: surface water contact angle is lower than 105 °

Wear resistance: the wear resistance of the obtained high-hardness anti-dazzle film is measured according to HGT 4303-.

Crackability: the protective film obtained by winding the protective film around a cylindrical mandrel bar according to the mandrel bar mandrel method used in the bending test of JIS K5600-5-1 was evaluated according to the mode of occurrence of cracks according to the following criteria:

o: winding to 10mm mandrel showed no cracks and was good.

X: the winding on a 10mm mandrel resulted in cracks. Analysis of Table 1 reveals that: the first to the eighth embodiments can meet the requirements of the anti-dazzle film on haze value, anti-dazzle property and antifouling property, and the hardness is more than 7H, the wear resistance is more than 600 times, and the requirements of physical properties are met. In addition, the amount of the adhesive resin, the leveling agent and the dispersing agent is adjusted, so that the influence on the overall performance of the anti-dazzle film is small and the anti-dazzle film meets the requirements; raising the temperature slightly reduces hardness and abrasion resistance, but does not affect performance requirements because the temperature is raised, solvent evaporation is accelerated, inorganic nanoparticles are rapidly "carried" to the coating surface, and the content of particles filled in the coating is reduced, resulting in a slight reduction in hardness and abrasion resistance.

For the same reason, as in examples three and four, within a certain range, increasing or decreasing the addition of inorganic nanoparticles will have a little influence on the hardness and wear resistance: the increase of the particle content causes slight poor curing due to an excessive content of the particles in the coating layer, resulting in a decrease in abrasion resistance; similarly, the particle content is reduced, and the rigidity does not reach the optimal state and the wear resistance is slightly reduced. But both of the above meet the performance requirements.

In contrast to comparative examples one to four, there were always some significant deficiencies in haze value and antiglare property. In the first comparative example, because the content of the inorganic nanoparticles is low, agglomeration phenomenon basically cannot occur, even if part of the inorganic nanoparticles are agglomerated, the inorganic nanoparticles are difficult to float to the surface of the coating, so that the inorganic nanoparticles are mainly filled in the coating, the hardness and the wear resistance are good, and the haze value and the anti-dazzle performance are difficult to meet the performance requirements. Similarly, in the second comparative example, the content of the inorganic nanoparticles is too high, the content of the dispersant and the leveling agent is low, the inorganic nanoparticles are easy to agglomerate, too much agglomerates form a concave-convex structure on the surface of the coating, so that the wear resistance is low, and the haze value cannot meet the performance requirement due to too high haze.

In addition, the temperature is too low, and the inorganic nano particles cannot agglomerate and float upwards in time in the volatilization process of the solvent, so that the anti-dazzle property cannot meet the performance requirement; and the temperature is too high, the solvent is volatilized too fast, so that the inorganic nano particles are completely agglomerated and float upwards, and the hardness and the wear resistance are obviously reduced. Furthermore, from comparative examples two and four, it can be seen that the hardness and abrasion resistance of the latter are even worse, which may be due to the fact that the solvent evaporation is accelerated by the high temperature, the agglomeration rate of the inorganic nanoparticles is further accelerated, and the agglomeration is irregular and disorganized, resulting in the inorganic nanoparticles after agglomeration having a very non-uniform particle size, and thus the hardness and abrasion resistance are significantly reduced.

Claims

1. A high-hardness anti-glare film comprises an anti-glare film laminated from top to bottom and having a concavo-convex shape on the surfaceThe anti-glare layer with the surface having the concave-convex shape is formed by coating an anti-glare coating on the transparent substrate to form a coating and then curing the coating, and is characterized in that the anti-glare coating is obtained by blending 15-45 parts by weight of adhesive resin, 5-20 parts by weight of inorganic nano particles, 9.5-67.8 parts by weight of solvent, 1-6 parts by weight of photoinitiator, 0.1-2 parts by weight of flatting agent, 0.1-3 parts by weight of dispersant and 0.1-2.5 parts by weight of anti-fingerprint auxiliary agent, the solid weight content of the anti-glare coating is 30-50%, and the coating amount of the coating after curing is 21g/m²-45 g/m²The curing process of the coating on the transparent substrate is as follows: firstly thermally curing for 30-180 s at 50-130 ℃, and then performing photo-curing by adopting ultraviolet irradiation with the energy of 100mJ/cm²The above.

2. The antiglare film as claimed in claim 1, wherein the adhesive resin is composed of 10-30 parts by weight of urethane acrylate with functionality greater than 5 and molecular weight of 1000-5000 and 5-15 parts by weight of urethane acrylate resin with functionality of 2-4 and molecular weight of 5000-20000 mixed together.

3. The high-hardness anti-glare film according to claim 1, wherein the inorganic nanoparticles are preferably amphiphilic inorganic nanoparticles with modified surfaces, the particle size is 50nm to 700nm, and the inorganic nanoparticles are one or more of aluminum oxide nanoparticles, silicon oxide nanoparticles, titanium oxide nanoparticles and zirconium oxide nanoparticles.

4. The high-hardness anti-glare film according to claim 1, wherein the solvent is any one of methanol, ethanol, isopropanol, n-butanol, t-butanol, PGME, ethylene glycol, acetone, methyl isobutyl ketone, cyclohexanone, butanone, hexane, cyclohexane, benzene, toluene, xylene, diethyl ether, and propylene glycol methyl ether, preferably methyl isobutyl ketone.

5. The antiglare film of claim 1, wherein the photoinitiator is one or more selected from 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl phenyl propyl ketone (1173), and 2, 4, 6-trimethyl benzoyl diphenyl phosphine oxide (TPO), preferably 1-3 parts by weight.

6. The high-hardness antiglare film according to claim 1, wherein the leveling agent is at least one of a fluorine-based leveling agent, a silicone-based leveling agent and an acrylic-based leveling agent, preferably a fluorine-based leveling agent.

7. The high-hardness anti-glare film according to claim 1, wherein the dispersant is an acrylic polymer dispersant for dispersing the inorganic nanoparticles and regulating the agglomeration of the inorganic nanoparticles, and is one or more of a chelate type copolymer, a block type copolymer or a blend type copolymer.

8. A high hardness anti-glare optical film according to claim 1, wherein the anti-fingerprint auxiliary is at least one of a perfluoropolymer, a fluoropolymer or a fluorocarbon-modified polymer.

9. A high hardness anti-glare optical film according to claim 1, wherein the thickness of the anti-glare layer having a concavo-convex shape on the surface is 15 μm to 30 μm, the thickness of the transparent substrate is 23 μm to 250 μm, preferably 125-250 μm; the transparent substrate is one of PET, TAC, SRF, PI, TPU and COP transparent substrates, and preferably PET transparent substrates.

10. A high hardness anti-glare optical film according to claim 1, wherein said coating layer has a coating amount after curing of preferably 25g/m²-35 g/m²The curing process is preferably as follows: heating at 50-130 deg.C for 30-180 s, and photocuring by ultraviolet irradiation with energy of180mJ/cm²The above.