TWI432794B - Anti - glare film with different internal and external haze and its making method - Google Patents

Description

Anti-glare film with different inner and outer haze and preparation method thereof

The invention relates to an anti-glare film, in particular to an anti-glare film with different inner and outer haze and a preparation method thereof.

With the advancement of optoelectronic technology, the research of anti-reflective optical film has become an important development technology. The study of anti-reflective optical films is widely used in the field of optics. The surface of optical components is coated with an anti-reflection film to enhance the overall performance of the optical instrument. In recent years, liquid crystal displays (LCDs) have been widely used in various modern electronic products such as personal computers, notebook computers, digital cameras, mobile phones, PDAs, and liquid crystal televisions (LCD TVs). Since the external light will reflect about 4~5% of the surface of the glass or plastic substrate on the surface of the display, the liquid crystal display is easily interfered by external light when it is used, which affects the visual effect of the screen. For large-sized panels, For LCD TVs larger than 20 inches, the effect of light reflection on the surface of the screen is more obvious. In order to solve the interference of external light, the anti-glare film is widely used in the liquid crystal display screen of notebook computers and computers due to obvious effects and low cost.

1 is a schematic view showing the structure of an anti-glare film according to a conventional technique. The anti-glare film is added by anti-glare particles to achieve an anti-glare effect, as shown in the figure: the anti-glare film structure comprises a substrate 1 and a setting. An anti-glare film coating 2 on the substrate 1 , the anti-glare film coating 2 comprising a resin 3 and a light-scattering particle 4, which is prepared by applying an anti-glare film coating solution to the substrate On the material 1, the solvent contained in the anti-glare coating liquid is evaporated through an oven. After the ultraviolet lamp is irradiated or ovend, the resin 3 in the anti-glare film coating solution is hardened to form the anti-glare film coating 2. The light-scattering particles 4 in the anti-glare film coating layer 2 are uniformly dispersed in the anti-glare film coating liquid when the anti-glare film coating liquid is just coated on the substrate 1, when the anti-glare film coating liquid is used After the solvent is evaporated, the resin 3 and the light-scattering particles 4 gradually settle to form the anti-glare film coating 2. Since the solvent of the anti-glare film coating liquid evaporates, the force between the solvent and the resin 3, the solvent and the light-scattering particles 4, and the resin 3 and the light-scattering particles 4 is complicated, so that the light-scattering particles 4 are dried. It is then randomly distributed in the anti-glare film coating 2. However, the above technique cannot control the distribution of the light-scattering particles 4 in the anti-glare film coating 2, and the haze of the anti-glare film cannot be effectively controlled. "Anti-glare hard coat film and process for producing the film", U.S. Patent No. 6,017,176, "Antiglare film and use thereof", U.S. Patent Publication No. 6613426B2, "Very fine anti" - glare hard coat film", "Anti-glare film and process for producing same thereof", US Patent Publication No. 6,696,140 B2, "Anti-glare hard coat film", US Patent Publication No. 6,896,960, US Patent Publication No. 7033638B2 The disclosure of "Antiglare film and process for producing the same" discloses various methods or materials for making an anti-glare film, which mainly utilizes the size and number of light-scattering particles and the thickness of the resin layer to control the resistance. The haze of the glare film. In addition, the anti-glare film of the Republic of China Patent No. 557363, the method of forming an anti-glare anti-reflection film of the Republic of China Patent No. 590886, and the optical anti-glare of the Republic of China Patent Notice No. M252022 The film, which also discloses a method and material for controlling the haze of the anti-glare film by using the size and number of light-scattering particles and the thickness of the resin layer.

However, due to the limitations of coating equipment, it is not an easy task to adjust the coating process. situation. Therefore, in order to produce anti-glare films with different haze, the anti-glare coating liquid formulation needs to be redesigned, and it is not easy to make due to factors such as wet film thickness, optical coating liquid viscosity, and the compatibility of light-scattering particles and resin. An anti-glare film with an inner and outer haze value designed.

The technique disclosed in "manufacturing process of embossed roll" of Japanese Patent No. 2006-088643 and "Antiglare film process for producing the same, and display device using antiglare film" by embossing The roller forms a concave and convex microstructure on the surface of the coating film to achieve anti-glare or anti-reflection effects. Although the anti-glare film of different haze can be produced by the above technology, the manufacture of different haze anti-glare films must be matched with different embossing rollers, resulting in an increase in cost. In addition, the above method can only change the external haze and cannot effectively adjust the internal haze.

The main object of the present invention is to solve the problem that the conventional technique cannot effectively control the inside and outside haze of the anti-glare film separately.

Another object of the present invention is to provide an anti-glare film which is simple in preparation and low in cost.

In order to achieve the above object, the present invention provides an anti-glare film having different inner and outer haze, comprising a transparent substrate and an anti-glare coating formed by coating an anti-glare coating on the transparent substrate, wherein the anti-glare coating The glare coating solution comprises a resin, a solvent, an initiator/hardener which hardens the resin, a resin light scattering particle and a resin light scattering particle.

In addition, the present invention also provides a method for preparing an anti-glare film with different internal and external haze, which comprises five steps of S1-S5, as listed below: S1: washing a transparent substrate and drying for use; S2: preparing a light scattering particle; S3: preparing an inverse characteristic light scattering particle, and modifying the light scattering particle prepared in step S2 into a pair of resin by surface modification The anti-characterization light scattering particles having different affinity characteristics; S4: preparing an anti-glare coating liquid, and the light scattering particles prepared in steps S2 and S3 and the inverse characteristic light scattering particles are placed in a resin at a desired ratio The anti-glare coating liquid is obtained in the middle; and S5: the anti-glare coating liquid prepared in step S4 is applied onto the transparent substrate of step S1 and dried to complete the production of the anti-glare film.

It should be particularly noted that the light scattering particles in the step description may be pro-resin light scattering particles or resin light scattering particles, and it is not limited to prepare the resin light scattering particles or the resin light scattering particles first, and the inverse characteristics. The light-scattering particles are resin-transparent light-scattering particles or pre-resin light-scattering particles having characteristics different from those of the light-scattering particles prepared first.

As apparent from the above description, the present invention controls the internal and external haze of the anti-glare film by adjusting the proportional concentrations of the resin-resistant light-scattering particles and the resin-removing light-scattering particles provided in the resin, thereby producing an anti-glare that meets different needs. The film has the same internal material as the resin light scattering particles and the resin light scattering particles, and has only the surface functional groups, which has the advantages of easy preparation and low cost.

Conventional technology

1‧‧‧Substrate

2‧‧‧Anti-glare coating

3‧‧‧Resin

4‧‧‧Light scattering particles

this invention:

10‧‧‧Transparent substrate

20a, 20b‧‧‧Anti-glare coating

30‧‧‧Resin

40a, 40b‧‧‧Pro-resin light scattering particles

50a, 50b‧‧‧ resin light scattering particles

51a, 51b‧‧‧ alienation

Figure 1 is a schematic view showing the structure of an anti-glare film of the prior art.

Figure 2 is a schematic cross-sectional view of a preferred embodiment of the present invention.

Figure 3 is a schematic cross-sectional view showing another preferred embodiment of the present invention.

4 is a flow chart showing the steps of a preferred embodiment of the present invention.

The detailed description and technical content of the present invention will now be described with reference to the following drawings: Referring to FIG. 2, it is a schematic cross-sectional view of a preferred embodiment of the present invention. As shown in the figure: the present invention is a different internal and external. The anti-glare film of haze comprises a transparent substrate 10 and an anti-glare film coating 20a formed by coating an anti-glare film on the transparent substrate 10, wherein the anti-glare coating liquid comprises a resin 30 a solvent, an initiator for curing the resin 30, a resin light scattering particle 40a and a resin light scattering particle 50a, wherein the initiator can also be replaced by a hardener, and the resin 30 can also be obtained. Hardening effect.

Further, the transparent substrate 10 is selected from the group consisting of glass, polyacrylate, polycarbonate, polyethylene, polyethylene terephthalate, and A group consisting of triacetyl cellulose or a combination thereof. The resin 30 is selected from the group consisting of a photocurable resin selected from the group consisting of a monomer and an oligomer, and a thermosetting resin selected from the group consisting of a monomer and an oligomer. Isobutyl acrylate, 2-ethylhexyl acrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate , trimethylolpropane diacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate, the oligomer is selected From urethane (meth) acrylate oligomer, polyester methacrylate a group of epoxy (meth) acrylate oligomers; the thermosetting resin is any one or a mixture of an inorganic resin and an organic resin, and the inorganic resin contains a methoxy group. Tetramethyloxysilane, Tetraethyloxysilane (TEOS) and Poly(ethyl silicate), which are any of acrylic resin and epoxy resin. .

The initiator is selected from the group consisting of benzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl 2-hydroxy-2-methyl-1-phenyl-1-propanone, methyl benzoylformate, and triarylsufonuium hexafluoro -antimonate salts).

The hardener is selected from the group consisting of hydrogen chloride, nitric acid, ammonia, 2-2-Azobis (isobutyronitrile, AIBN), azobisisoheptyl (2,2'-Azobis (2,4). -dimethylvaleronitrile), ADVN), Benzoyl peroxide (BPO), Methyl tetrahydrophthalic anhydride, Diethyltriamine and Dicyandiamide The group that makes up.

Further, the pre-resin light-scattering particles 40a and the resin-repellent light-scattering particles 50a are any one of organic particles and inorganic particles selected from the group consisting of silicon oxide, aluminum oxide, and Antimony-doped tin oxide, tin oxide, zinc antimonite, antimony pentoxide, indium tin oxide, and aluminum-doped zinc oxide (indium tin oxide) Aluminum-doped zinc A group consisting of oxide, zinc antimonate), the organic particles may be a group consisting of polymethyl methacrylate (PMMA), polystyrene, and benzoguanamine.

The solvent material is selected from the group consisting of isopropanol (IPA), methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ethyl acetate (EAC), butyl acetate (BAC), toluene, and ring. a group consisting of cyclohexanone, methanol, and propylene glycol monoethyl ether acetate (PGMEA).

The pre-resin light-scattering particles 40a produced as described above have surface functional groups different from the resin-transparent light-scattering particles 50a, and in the present embodiment, the resin-repellent light-scattering particles 50a are the resin-releasing light-scattering particles 40a. As a result of the surface modification, the resinized light-scattering particles 50a include the hydrophilic resin light-scattering particles 40a and an alien layer 51a formed on the outer surface of the resin-light-scattering particles 40a. The size of the resin-light-scattering particle 40a and the resin-coated light-scattering particle 50a is between 0.5 and 10 μm, and more usually 1 to 5 μm. Since the resin-light-scattering particle 40a does not repel the resin 30, it is immersed in The anti-glare film coating 20a is internally, and in contrast, the resin-repellent light-scattering particles 50a are dispersed in the surface layer of the anti-glare film coating 20a because the resin 30 is relatively repelled, by adjusting the resin-light-scattering particles 40a and the The concentrations of the resin light-scattering particles 50a control the inner haze and the outer haze, respectively.

Please refer to FIG. 3 again, which is a schematic cross-sectional view of another preferred embodiment of the present invention. The difference between FIG. 2 and the second embodiment is that the resin-repellent light-scattering particles 50b have a concentrated attraction force and gather with each other. Forming a larger aggregate in the anti-glare film coating 20b, and the aggregate protrudes from the surface of the anti-glare film coating 20b, so that the surface of the anti-glare film coating 20b is uneven, thereby controlling Outside haze. Similarly, the resin light scattering particles 50b comprise the resin light scattering particles 40b and a The hydrophilic resin scatters the alien layer 51b on the outer surface of the particle 40b.

The present invention also provides a method for fabricating an anti-glare film with different internal and external haze. Referring to FIG. 4, it is a schematic flow chart of a preferred embodiment of the present invention. The manufacturing method includes five S1~S5 processes. The steps are as follows: S1: washing a transparent substrate and drying for use; S2: preparing a light scattering particle; S3: preparing an inverse characteristic light scattering particle, and scattering the light prepared in step S2 by surface modification The particles are modified into anti-characteristic light-scattering particles having different affinity characteristics to the resin, and the inverse-state light-scattering particles include the light-scattering particles and an anti-characteristic layer formed on the outer surface of the light-scattering particles; S4: making one The anti-glare coating liquid, the light scattering particles prepared in steps S2 and S3 and the inverse characteristic light scattering particles are placed in a resin in a desired ratio to obtain the anti-glare coating liquid; and S5: the step The anti-glare coating liquid prepared in S4 is applied onto the transparent substrate of step S1 and dried to complete the production of the anti-glare film.

It should be particularly noted that the light scattering particles in the step description may be pro-resin light scattering particles (40a, 40b) or resin light scattering particles (50a, 50b), and it is not necessary to prepare the resin light scattering particles (40a). 40b) or first to prepare resin light scattering particles (50a, 50b), and the inverse characteristic light scattering particles refer to resin light scattering particles (50a, 50b) or resin light which are different from the characteristics of the light scattering particles prepared first. Scattering particles (40a, 40b). In the case of preparing the resin-reducing light-scattering particles (40a, 40b), the anti-characteristic layer can be the aforementioned alien layer (51a, 51b), thereby achieving the characteristics of intimacy and dissimilarity.

In summary, the present invention adjusts the ratio of the resin light scattering particles (40a, 40b) disposed in the resin 30 and the resin light scattering particles (50a, 50b). The example concentration controls the inner and outer haze of the anti-glare film, respectively, thereby producing an anti-glare film that meets various requirements, and the resin-light-scattering particles (40a, 40b) and the resin-repellent light-scattering particles (50a, 50b) The internal materials are the same, and only their surface functional groups are different, which has the advantages of easy preparation and low cost. Therefore, the present invention is highly progressive and conforms to the requirements of the invention patent application, and the application is made according to law, and the praying office grants the patent as soon as possible.

The invention can be further illustrated by the following preferred embodiments: substrate pretreatment: a PET substrate is washed with ethanol, washed with deionized water, and dried for use.

Production of the resin-resistant light-scattering particles and the resin-based light-scattering particles: 0.86 g of PVP-40 (manufactured by SIGMA-ALDRICH) and 32 ml of ethanol were mixed for 1 hour, and then 8 ml of Styrene (SIGMA) in which 1 wt% of AIBN (manufactured by SHOWA Co., Ltd.) was dissolved was added. - ALDRICH company made a monomer, and placed in a three-neck round bottom flask containing a heated reflux device, followed by nitrogen for 30 minutes to remove oxygen, and finally the oxygen-removed articles were placed in a constant temperature water bath to evenly stir, the reaction temperature of the constant temperature water bath At 70 ° C, the reaction time was 24 hours to obtain a milky liquid, and the emulsion liquid was washed several times by centrifugation and then dried to obtain a white powder of resin-resistant light-scattering particles. The particle size distribution measured by a metallographic microscope (MICROTECH-835) was approximately 3.4-3.6 microns.

Take 1g of pro-resin light scattering particles in a 60ml sample bottle and add 10ml of industrial ethanol, then vortex for 10 minutes with ultrasonic wave, then take about 2-2.5ml of sulfuric acid and slowly add it to the bottle until the pH value in the bottle is equal to 0.25. Left and right, then oscillate with ultrasonic for 10 minutes. Finally, place the whole cup of the solution in a water bath at 70 ° C for 3 hours, centrifuge and wash and dry to obtain the resin light scattering particles.

Three different embodiments are listed below to enhance the features of the invention:

Example 1: 0.6 g of the resin light scattering particles were added to 4 g of isobutanol and dispersed by ultrasonic vibration. Further, 5 g of pentaerythritol triacrylate resin (manufactured by Sartomer Co., Ltd.) and 0.4 g of Irgacure 184 (manufactured by Ciba-Geigy Co., Ltd.) were added, and dispersed by ultrasonic vibration. The resulting coating liquid was coated on a polyethylene terephthalate (PET) substrate with a RDS No. 5 coating bar, and then baked in an oven at 70 ° C for 3 minutes, followed by an H-type mercury lamp (dosage of 500). ~600 mJ/cm2) Irradiation hardens to form an anti-glare film.

Example 2: 0.6 g of the resin-releasing light scattering particles were added to 4 g of isobutanol and dispersed by ultrasonic vibration. Further, 5 g of pentaerythritol triacrylate resin (manufactured by Sartomer Co., Ltd.) and 0.4 g of Irgacure 184 (manufactured by Ciba-Geigy Co., Ltd.) were added, and dispersed by ultrasonic vibration. The resulting coating liquid was coated on a polyethylene terephthalate (PET) substrate with a RDS No. 5 coating bar, and then baked in an oven at 70 ° C for 3 minutes, followed by an H-type mercury lamp (dosage of 500). ~600 mJ/cm2) Irradiation hardens to form an anti-glare film.

Example 3: 0.3 g of the resin light scattering particles and 0.3 g of the resin light scattering particles were added to 4 g of isobutanol, and dispersed by ultrasonic vibration. Further, 5 g of pentaerythritol triacrylate resin (manufactured by Sartomer Co., Ltd.) and 0.4 g of Irgacure 184 (manufactured by Ciba-Geigy Co., Ltd.) were added, and dispersed by ultrasonic vibration. The resulting coating liquid was coated on a polyethylene terephthalate (PET) substrate with a RDS No. 5 coating bar, and then baked in an oven at 70 ° C for 3 minutes, followed by an H-type mercury lamp (dosage of 500). ~600 mJ/cm2) Irradiation hardens to form an anti-glare film.

The measurement results of total light penetration and total haze and internal and external haze by haze meter NDH-5000W (labeled as Nippon Denshoku) are shown in Table 1: Table 1. Haze measurement results

It can be seen from the above table that the inner and outer haze of the anti-glare film can be effectively adjusted by the resin-light-scattering particles and the resin-repellent light-scattering particles disposed at different concentrations.

The present invention has been described in detail above, but the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the scope of the invention. That is, the equivalent changes and modifications made by the scope of the present application should remain within the scope of the patent of the present invention.

10‧‧‧Transparent substrate

20a‧‧‧Anti-glare coating

30‧‧‧Resin

40a‧‧‧Pro-resin light scattering particles

50a‧‧‧Resin light scattering particles

51a‧‧‧Sparse layer

Claims (9)

An anti-glare film having different inner and outer haze, comprising: a transparent substrate; an anti-glare film coating formed by coating an anti-glare film on the transparent substrate; the anti-glare coating liquid comprises a resin a solvent, an initiator for curing the resin, a resin light scattering particle, and a resin light scattering particle, the resin light scattering particle comprising the resin light scattering particle and a light formed in the resin An alien layer that scatters the outer surface of the particle. An anti-glare film having different inner and outer haze, comprising: a transparent substrate; an anti-glare film coating formed by coating an anti-glare film on the transparent substrate; the anti-glare coating liquid comprises a resin a solvent, a hardener for hardening the resin, a resin light scattering particle and a resin light scattering particle, the resin light scattering particle comprising the resin light scattering particle and a light scattering formed by the resin An alien layer on the outer surface of the particle. An anti-glare film having different internal and external haze as described in claim 1 or 2, wherein the pro-resin light-scattering particles are immersed in an anti-glare film coating, and the resin-transparent light-scattering particles are dispersed in an anti-glare film coating. Layer surface layer. The anti-glare film of different internal and external haze as described in claim 1 or 2, wherein the resin-repellent light-scattering particles have a collecting attraction force with each other, and aggregate with each other to form a large aggregate in the anti-glare film coating. . The anti-glare film of different internal and external haze as described in claim 1 or 2, wherein the resin is selected from the group consisting of a photocurable resin and a thermosetting resin. An anti-glare film having different internal and external haze as described in claim 1 or 2, wherein the pro-resin light The scattering particles and the resin-repellent light-scattering particles are any one of organic particles and inorganic particles selected from the group consisting of cerium oxide, aluminum oxide, antimony doped tin dioxide, tin oxide, zinc telluride, antimony pentoxide, A group consisting of indium tin oxide and aluminum-doped zinc oxide, the organic particles may be a group consisting of polymethyl methacrylate, polystyrene, and benzoguanamine. The anti-glare film of different internal and external haze as described in claim 1 or 2, wherein the pro-resin light-scattering particles and the resin-removing light-scattering particles have a size of 0.5 to 10 um. The invention relates to a method for preparing an anti-glare film with different inner and outer haze, which comprises the steps of: washing a transparent substrate and drying it for use; preparing a light-scattering particle; and modifying the light-scattering particles prepared by surface modification by surface modification The reverse-characteristic light-scattering particle having a different affinity characteristic of the resin, the anti-characteristic light-scattering particle comprising the light-scattering particle and an anti-characteristic layer formed on a surface of the light-scattering particle; the light-scattering particle And the anti-characterization light scattering particles are placed in a resin to obtain an anti-glare coating liquid; and the anti-glare coating liquid is applied onto the transparent substrate and dried to complete the production of the anti-glare film. The method for producing an anti-glare film having different internal and external haze according to claim 9 , wherein the anti-glare coating liquid is selected from the group consisting of dip coating, spin coating, and wire coating. A group of slit coating and gravure coating is applied to the transparent substrate.