TWI554780B - A method for producing anti-reflective film - Google Patents

Description

Method for preparing antireflection film

The present invention relates to a method for preparing a film, and more particularly to a method for preparing an antireflection film.

In recent years, with the rise of touch-screen and large-size panels, the demand for anti-reflection films has gradually increased in the market. Anti-reflection films can be used in building glass, automotive windows, optical instruments, etc. The anti-reflection film reduces the reflected light generated by the light on the surface of a specific object, and avoids the influence of the object due to light interference. In view of the wide application and high practicality of the anti-reflection film, the research and development of the anti-reflection film are in full swing. The ground is in progress.

A conventional anti-reflection film is prepared by depositing a conventional anti-reflection film on the surface of an object by a vacuum coating method. Although the conventional anti-reflective film has excellent uniformity and performance by the preparation method of the conventional anti-reflection film, it is well known that the vacuum coating method has high technical threshold, expensive equipment, and long deposition time. The cost of the conventional anti-reflection film obtained is high. Moreover, the preparation method of the conventional anti-reflection film is only suitable for bonding the conventional anti-reflection film to a flat object, when the surface of the object is presented. In the case of irregularities, the uniformity of the conventional antireflection film is greatly reduced, and thus the applicability of the conventional antireflection film preparation method is limited.

In view of the above, it is necessary to provide a method for preparing an anti-reflection film to solve the problems in the preparation method of the conventional anti-reflection film, and the vacuum coating method used is costly and limited in application.

The invention provides a method for preparing an anti-reflection film, which is an anti-reflection film formed on the surface of a substrate by a simple process of the layer stacking method.

The present invention provides a method for producing an antireflection film which is capable of forming the antireflection film on a substrate having a non-flat surface.

The method for preparing an anti-reflection film of the present invention comprises: a substrate providing step of providing a substrate; and a polymer base film forming step of forming a first charge on the surface of the substrate by using a first charge polymer solution a polymer film, wherein a second charge polymer film is formed on the surface of the first charge polymer film by a second charge polymer solution, so that the first charge polymer film and the second charge polymer film are formed together a polymer base film; a polymer base film stacking step, the first charge polymer solution is formed on the surface of the second charge polymer film to form another first charge polymer film, and the second charge polymer solution is continued Forming another second charge polymer film on the surface of the first charge polymer film to form a polymer base film on the surface of the polymer base film; repeating the polymer base film stacking step in a repeated step, Up to several layers of the polymer base film jointly forming a polymer film on the surface of the substrate, the polymer film having a thickness of at least 20 nm; and a cerium oxide precipitation step, using a cerium oxide precursor liquid to the high score The cerium oxide is precipitated in the submembrane.

The method for preparing an antireflection film of the present invention further comprises a polymer film removing step of removing the polymer film after the ceria precipitation step.

The method for preparing an antireflection film according to the present invention, wherein the first charge polymer solution comprises a first charge polymer and a first solvent, the first charge polymer having an amine group, a mercapto group or an imidazolyl group The second charged polymer aqueous solution comprises a second charge polymer and a second solvent, and the second charge polymer has a carboxyl group, a phosphoric acid group or a sulfuric acid group.

In the method for producing an antireflection film of the present invention, the first charge polymer is a polymer grafted with a hydrocarbon group, or the first charge polymer is a block polymer.

The method for preparing an antireflection film of the present invention, wherein the first charge polymer is a poly The lysine is grafted with citric acid, the graft ratio of the first charge polymer is 0.2 to 0.4, and the second charge polymer is polylysine.

In the method for preparing an antireflection film of the present invention, the first charge polymer is polylysine-block-polystyrene, and the second charge polymer is polyamic acid.

The method for preparing an antireflection film of the present invention, wherein the first charge polymer solution has a pH of 4 to 7.5.

The method for preparing an antireflection film of the present invention, wherein the substrate is glass, polymethyl methacrylate, polycarbonate, indium tin oxide conductive glass, polyethylene terephthalate or aluminum oxide.

The method for preparing an antireflection film of the present invention, wherein the cerium oxide precursor liquid system comprises a cerium oxide precursor, the cerium oxide precursor is a compound having a tetraoxindole group or a compound having a trioxane group. .

In the method for preparing an antireflection film of the present invention, an antireflection film is obtained by a method for preparing an antireflection film, and the antireflection film has a thickness of 80 to 160 nm.

The method for preparing the anti-reflection film of the present invention is a solution process in which the first charge polymer film and the second charge polymer film layer are alternately stacked, and the steps are simple and do not need to use a large, precise, expensive and energy-consuming basis. The stage can be carried out. Compared with the vacuum coating method which is conventionally used for preparing an anti-reflection film, the present invention can greatly simplify the process of the anti-reflection film, thereby achieving the effect of reducing the process cost of the anti-reflection film.

The anti-reflection film of the present invention is prepared by treating the substrate with the first charge polymer, the second charge polymer and the ceria precursor in a liquid state, so that the substrate surface can be formed in various shapes. The anti-reflection film is formed thereon to further increase the applicability of the anti-reflection film obtained.

Fig. 1a is a layer-thickness diagram of the anti-reflection film group A1a to A5a obtained by the method for producing an antireflection film of the present invention.

Fig. 1b is a layer-thickness diagram of the anti-reflection film group A1b to A5b obtained by the method for producing an antireflection film of the present invention.

Fig. 2a is a SEM top view of the antireflection film obtained by the method for producing the antireflection film of the present invention.

Fig. 2b is a SEM cross-sectional view of the antireflection film obtained by the method for producing the antireflection film of the present invention.

Fig. 3 is a FTIR spectrum of a polymer film of the method for producing an antireflection film of the present invention.

Fig. 4 is an FTIR spectrum of an antireflection film obtained by the method for producing an antireflection film of the present invention.

Fig. 5 is a chart showing the breakthrough spectra of the antireflection film groups D1 to D3 and the control group obtained by the method for preparing the antireflection film of the present invention.

Fig. 6 is a chart showing the breakthrough spectra of the antireflection film group D3, D4 and the control group obtained by the method for producing the antireflection film of the present invention.

Fig. 7 is a chart showing the breakthrough spectra of the antireflection film group D5, D6 and the control group obtained by the method for producing the antireflection film of the present invention.

Fig. 8 is a chart showing the penetration spectra of the antireflection film groups D1, D3, D6, D7, and D8 and the control group obtained by the method for producing the antireflection film of the present invention.

Fig. 9 is a chart showing the penetration spectra of the antireflection film group E1 and the control group obtained by the method for producing the antireflection film of the present invention.

Fig. 10 is a photographic view of an antireflection film obtained by the method for producing an antireflection film of the present invention.

The above and other objects, features and advantages of the present invention will become more <RTIgt; The system includes: a substrate providing step, a high The molecular base film forming step, a polymer base film stacking step, a repeating step, and a cerium oxide precipitation step. A plurality of polymer base films are stacked on a surface of a substrate through a first charge polymer solution and a second charge polymer solution to form a polymer film and pass through a cerium oxide precursor solution. The polymer film is precipitated with cerium oxide, and a polymer film removing step may be further included, and the polymer film is removed after the cerium oxide precipitation step. Through the preparation method of the anti-reflection film of the present invention, an anti-reflection film is formed on the surface of the substrate.

The "first charge" and the "second charge" in the present invention are opposite charge types. For example, if the first charge is a positive charge, the second charge is a negative charge, and so on. First described.

In detail, the substrate providing step is for providing the substrate for supporting the growth of the polymer base film, and the substrate may be any material for forming the anti-reflection film on the surface thereof, for example, glass, Polymethyl methacrylate, polycarbonate, indium tin oxide conductive glass, polyethylene terephthalate or aluminum oxide, etc., wherein the substrate having the antireflection film can be further formed into a 3C product. The substrate, the automobile window, the lens, and the like, the substrate is preferably transparent; and in the method for preparing the anti-reflection film of the present invention, the anti-reflection film is formed on the substrate by a solution method, so the shape of the substrate is The shape may be any shape, such as a flat plate shape, an arc shape, or an irregular shape, and the material and shape of the substrate are not limited herein.

It is worth mentioning that a first charge polymer film is formed on the surface of the substrate by the first charge polymer, so that the first charge polymer film with uniformity can be formed on the surface of the substrate. Preferably, the surface of the substrate is provided with a second electric charge to facilitate the charge attraction of the substrate and the first charge polymer solution, and the first charge polymer film is smoothly generated on the surface of the substrate. Therefore, in order to improve the uniformity of the film formation of the first charge polymer film and to have a good adhesion between the subsequently formed anti-reflection film and the substrate, the film may be modified before the step of forming the polymer base film. The surface of the substrate is such that the surface of the substrate carries a second charge and a group which can form a hydrogen bond with the first charge polymer, and the modification method can be a plasma surface. Processing and other methods are not limited here.

In addition, in order to prevent the impurities on the surface of the substrate from affecting the adhesion between the anti-reflection film and the substrate, the first cleaning solution and the second cleaning solution may be sequentially cleaned to remove the substrate. Organic matter, oxide or metal ions on the surface of the substrate. In the first embodiment of the present invention, the substrate is made of glass, and the first purification solution comprises water, hydrogen peroxide (31% by weight) and ammonia (25% by weight), and is in a volume ratio. 5:1:1 mixture, the second purification solution comprises water, hydrogen peroxide and hydrochloric acid (36% by weight), and is mixed at a volume ratio of 5:1:1, the substrate is immersed in The first purification solution is removed for 5 minutes, and the organic matter and particles remaining on the surface of the substrate are removed by hydrogen peroxide in an alkaline environment, rinsed with water, and then the substrate is immersed in the second purification solution for 5 minutes to remove The metal ions on the surface of the substrate are used to obtain the substrate having a clean surface, and the polymer base film forming step is continued with the substrate.

The polymer base film forming step is to form the polymer base film on the surface of the substrate. In detail, the first charge polymer solution is first coated on the surface of the substrate to form the first charge polymer film, and then Applying the second charge polymer solution to the surface of the first charge polymer film to form the second charge polymer film, so that the first charge polymer film and the second charge polymer film together form the high Molecular base film. The first charge polymer solution comprises a first charge polymer and a first solvent, and the second charge polymer solution comprises a second charge polymer and a second solvent, wherein the substrate and the first charge are high The molecule has an opposite charge, and the first charge polymer and the second charge polymer have opposite charges. In the first embodiment of the present invention, the first charge polymer has a positive charge. The second charge polymer is negatively charged, and the substrate is slightly negatively charged. However, the charge of the first charge polymer and the second charge polymer can be adjusted according to the type of charge on the surface of the substrate. The examples are limited.

More specifically, the first charge polymer and the second charge polymer have at least one charged group positively or negatively charged, for example, the first charge polymer system of the embodiment has A positively charged amino group, a mercapto group or an imidazole group, the second charge polymer having a negatively charged carboxyl group, a phosphate group or a sulfuric acid group. Preferably, the first charge polymer may be a polymer of a grafted hydrocarbon group or a block type polymer, and since the porosity ratio of the antireflection film is positively correlated with antireflection efficiency, the The specific composition and configuration of the first charge polymer increases the porosity of the anti-reflective film that is subsequently formed. For example, in the first embodiment of the present invention, the substrate is made of glass, and the first charge polymer is poly(L-lysine-graft-Decanoyl, PLD for short). The second charge polymer is poly(L-glutamic acid, PGA for short). In the second embodiment of the present invention, the substrate is made of PMMA, and the first charge polymer is Poly-L-lysine-block-polystyrene (PLL-b-PS), and the second charge polymer is poly-proline.

In the first embodiment of the present invention, the graft ratio of the first charge polymer is 0.2 to 0.4 (the graft ratio described herein is calculated from the ratio of the NMR signals of the PLD), and the first The pH of the charge polymer solution is 4 to 7.5, so that the first charge polymer can form a vesicle in the first solvent, and when the first charge polymer solution is coated on the surface of the substrate The microcell line formed by the first charge polymer expands, with the charged group facing outward, and the remaining uncharged neutral groups (such as the long carbon chain) form a double layer inward, and The sunflower acid grafted by the first charge polymer can cause a plurality of stereoscopic spaces when the first charge polymer adheres to the substrate, and has a plurality of holes in the first charge polymer film formed later. When the antimony oxide film is formed and the antireflection film is formed, the antireflection film has a good antireflection performance because it has a plurality of holes.

In addition, the size of the micelle is about 40 to 200 nm, and the size of the micelle can be adjusted according to the graft ratio and pH. Moreover, the pH of the first charge polymer solution is preferably 5, so that the micelles in the first charge polymer solution can be stably present, and the PLD dielectric potential of pH 5 is compared with pH 7.4. Higher, so that the PLD is stacked on the substrate in a looser arrangement, forming The first charge polymer film has a high porosity, and the surface of the first charge polymer film formed has an appropriate pH value to avoid affecting the formation of the second charge polymer film (PGA will be Dissolved in an environment with a pH of less than 4. In order to enable the microcell to be smoothly produced to facilitate the subsequent generation of the antireflection film having porosity, before the first charge polymer is dissolved in the first solvent, the PLD may be first dissolved in methanol and then dialyzed. Prepare PLD micelles; in detail, PLD is dissolved in methanol at a concentration of 1 mg/ml, and PLD methanol solution is placed in a 6000-8000 MW dialysis bag, and 1500 ml of 0.01 N PBS is dialyzed and replaced after a specific time. The PBS is repeatedly dialyzed to obtain a PLD microcell, and then the PLD microcell is dissolved in the first solvent to obtain the first charged polymer solution. The first solvent in the embodiment is water.

In a second embodiment of the present invention, the first solvent is water, and the first charge polymer naturally forms PLL-b-PS in water with a hydrophilic end (NH3+) facing outward and a hydrophobic end facing inward. The microcells, according to the mechanism in the first embodiment, form a plurality of holes in the subsequently formed first charge polymer film, and in the first charge polymer solution of the second embodiment, PLL-b-PS The stacking of the micelles is less sensitive to the influence of pH, and the pH of the first charged polymer solution can be expanded to 3 to 7.5.

In detail, the present invention forms the first charge polymer and the second charge polymer in a coating manner. When the first charge polymer solution is applied to the substrate, the first charge polymer is adsorbed on the surface of the substrate by charge attraction and hydrogen bonding force to form the first charge polymer film. When the di-charged polymer solution is applied to the surface of the first charge polymer film, since the first charge polymer and the second charge polymer have opposite charges, the charge is attracted to each other first. Forming a second charge polymer film on the surface of the charged polymer film, and further, the first charge polymer and the second charge polymer are naturally subjected to a hydrogen bond force between the amino acids to strengthen the first The charge polymer film is tightly bonded to the second charge polymer film. The term "coating" as used herein means that the first charge polymer solution or the second charge polymer solution is attached to a target surface by various methods. For example: the coating method can be For spin coating, dip coating, spray coating, etc., it is not limited herein. In the first embodiment of the present invention, the substrate is first immersed in the first charge polymer solution for about 10 minutes, and the substrate having the first charge polymer film is quickly immersed in a washing liquid to wash the residue. The first charge polymer solution is then immersed in the second charge polymer solution for 10 minutes to form the second charge polymer film, and after washing with the washing liquid, the polymer base film is formed on the surface of the substrate. . In this embodiment, the temperature of the first charge polymer solution and the second charge polymer solution is normal temperature (25 to 35 ° C), but those having ordinary knowledge in the technical field of the invention may rely on the first charge polymer The temperature of the second charge polymer is adjusted, and the present invention is not limited.

The polymer base film stacking step is performed by stacking another polymer base film on the surface of the polymer base film. In detail, the polymer base film stacking step comprises: forming another first charge polymer film on the surface of the second charge polymer film by using the first charge polymer solution, and continuing the second charge polymer solution Forming another second charge polymer film on the surface of the first charge polymer film to form a polymer base film on the surface of the polymer base film, the first charge polymer film and the second charge polymer The film forming mechanism is the same as the above-described polymer base film forming step, and will not be described here.

After forming two layers of the polymer base film on the surface of the substrate, the repeating step is performed. The repeating step is a step of repeatedly performing the polymer base film stacking step of stacking the first layer of the first charge polymer film and the second charge polymer film formed by the coating solution until the polymer film is formed on the surface of the substrate. The polymer film comprises a plurality of layers of the polymer base film, and the polymer film has a thickness of at least 20 nm. Herein, since the subsequent cerium oxide is precipitated in the polymer film to form the anti-reflective film, and the anti-reflective effect of the anti-reflective film is related to the thickness, the polymer film must reach a specific thickness. If the thickness of the polymer film is less than 20 nm, the anti-reflection film formed subsequently cannot have a significant anti-reflection effect.

After preparing the polymer film having a specific thickness, the cerium oxide is performed. The precipitation step, that is, the cerium oxide is precipitated in the polymer film by the cerium oxide precursor liquid, and the anti-reflection film is formed. In the present invention, the cerium oxide can be precipitated into the polymer film in various manners by using the cerium oxide precursor liquid, for example, the cerium oxide precursor liquid is attached to the polymer film by coating or immersion. It is preferably sprayed or immersed to enhance the uniformity of adhesion of the cerium oxide precursor to the polymer film. The cerium oxide precursor liquid has a cerium oxide precursor, and the cerium oxide precursor system may be a compound having a tetraoxindole group or a compound having a trioxane group, which can form a cerium oxide by a chemical reaction. The compound is not limited to the above categories. In the first embodiment of the present invention, the substrate having the polymer film is placed in a tetramethyl orthosilicate (TMOS) having a molar concentration of 0.35 M for two hours, and the cerium oxide is precipitated in the polymer film. .

When the cerium oxide precursor liquid precipitates cerium oxide, the -Si(OH)4 group in the cerium oxide precursor liquid naturally reacts with the positively charged group of the first charge polymer in the polymer film. In the first embodiment of the present invention, the positively charged group is an amine group to generate a condensation reaction, so that the polymer film has a positively charged group to precipitate and form cerium oxide, because a plurality of the first charges are high. The molecular film has a plurality of pores, and the cerium oxide is grown along the first charged polymer film (along the amine or the surface of the first charge polymer), so the anti-reflective film is formed. Preferably, the thickness of the anti-reflection film formed by the preparation method of the anti-reflection film of the present invention is about 80-160 nm, so that the anti-reflection film can simultaneously achieve light transmittance while avoiding light reflection. The anti-reflection film can be widely applied to various fields when the substrate is transparent.

After the cerium oxide is precipitated in the polymer film, the method for preparing the antireflection film of the present invention may further comprise the polymer film according to the type of the substrate, the first charge polymer, the second charge polymer, and the subsequent use. The removing step further removes the polymer film in the substrate in which the cerium oxide is precipitated, and enhances the porosity in the anti-reflecting film. For example, it can be heated and sintered to the decomposition temperature of the polymer film, and the polymer is naturally decomposed in a high temperature environment to remove the polymer film. However, the method of removing the polymer film is not limited thereto. For example: in the present invention In one embodiment, the substrate is made of glass, and the glass is suitable for further sintering because of high heat resistance. Therefore, the substrate subjected to the ceria precipitation step can be sintered at 550 ° C for 8 hours, thereby removing the height. Molecular film, but in the second embodiment, the substrate material is PMMA, and it is not suitable for heating and removing the polymer film. It should be noted here that whether or not the polymer film is removed, the cerium oxide precipitated on the substrate has an anti-reflection effect on the surface of the substrate.

Therefore, in the present invention, the first charge polymer solution and the second charge polymer solution are interleaved to form a plurality of the first charge polymer film and the second charge polymer film on the substrate, so that several The polymer base film is stacked on the substrate to jointly form the polymer film having a thickness of at least 20 nm, and the ceria precursor is used to precipitate cerium oxide in the polymer film, and the polymer may be further included. A film removal step to further remove the polymer film on the surface of the substrate. The anti-reflection film is disposed on the surface of the substrate, and has the effect of improving the anti-reflection performance of the substrate. Further, the deposition of the polymer film and the cerium oxide is carried out by a solution process, which can be prepared not only by a simple operation procedure but also by a simple operation step. The anti-reflection film also allows the anti-reflection film to be formed on the surface of the substrate of various shapes.

In order to confirm that the preparation method of the antireflection film of the present invention can be used to prepare an antireflection film having antireflection performance, the following tests are carried out:

(A) Relationship between the number of stacked layers and the thickness of the polymer film

In this test, the thickness of the polymer film under different stacking layers is measured by a film measuring instrument, and the thickness of the polymer film is simulated by the destructive interference spectrum generated by the reflection and refraction of the received light in the polymer film. The test is carried out by measuring the polymer film formed in the first embodiment, wherein PLDs having different monomer repetition numbers and graft ratios are used as the first charge polymer, and the first charge polymer solution is controlled. The pH values were 5 and 7.4, and the layer-thickness analysis obtained was as shown in Figures 1a and 1b, respectively, and the respective groups are detailed in Table 1. The number of layers is the number of the polymer base film.

Table 1: Test (A) correspondence table of each group

Referring to Figures 1a and 1b, regardless of the monomer number of the first charge polymer, the graft ratio, and the pH of the first charge polymer solution, the thickness of the polymer film is equal to the number of stacked layers. Positive correlation, that is, as the number of stacked layers increases, the thickness of the polymer film grows. It can also be observed from the figure that when the number of layers of the polymer base film stack is four, the thickness of the polymer film is about 20 nm, which is the minimum thickness requirement of the polymer film as defined in the present invention.

(B) Porosity of the antireflection film

In this test, a polymer film having a stacking layer of 8 layers in the A5a group is taken, and the precipitation of cerium oxide is continued, and after the polymer film is removed by sintering, the obtained antireflection film is photographed by a scanning electron microscope. The top view and the cross-sectional view of the image are shown in Figures 2a and 2b, respectively. The SEM image clearly shows that there are several holes in the anti-reflection film, that is, the anti-reflection film has porosity.

Further, the anti-reflection film prepared by different kinds of the first charge polymer and the first charge polymer solution of different pH values was measured for the relationship between the porosity and the refractive index and the pH value and is shown in Table 2 below. The first charge polymer in the B1 to B2 group is a monomer repeat number of 170, a graft ratio of 0.2 PLD, and the first charge polymer of the B3 to B5 group is PLL-b-PS. Among them, the porosity (P) value is obtained by measuring the refractive index (np) of the hole material and the refractive index (n) of the material itself, and is calculated by the formula (1).

(n _p ² -1)/(n ² -1)=1-p/100 (1)

It can be seen from Table 2 that when the first charge polymer is PLD, the pH of the first charge polymer solution has a great influence on the porosity of the formed anti-reflection film, but when the first charge polymer is a PLL In the case of -b-PS, the formation of the antireflection film is not affected by the pH value, and the pH of the first charge polymer solution has a good porosity of 3 to 7.

(C) cerium oxide precipitation test

In this test, the polymer film and the antireflection film were analyzed by FTIR, and the analysis results are shown in Fig. 3 and Fig. 4, respectively. It can be clearly observed in Fig. 3 that there are obvious absorption peaks at 1623cm-1, 1645cm-1 and 1545cm-1. This signal is characteristic of the secondary structure formed by the first charge polymer and the second charge polymer. Figure 4 shows the precipitation of cerium oxide in the polymer film, and the FTIR spectrum of the anti-reflective film is measured without sintering. The symmetry absorption peak of Si-O-Si at 801 cm-1 is 1092. At 1207cm-1, it is a Si-O-Si asymmetric structure peak, and at 960cm-1, it is a Si-OH absorption peak. This absorption peak is a characteristic signal of cerium oxide. The analysis results of Figures 3 and 4 can It was confirmed that the preparation method of the antireflection film of the present invention can surely bond cerium oxide to the substrate by using a cerium oxide precursor.

(D) Measurement of penetration rate of antireflection film prepared by the first embodiment

Since the reflectance is affected by the surface roughness, the measurement results cannot faithfully reflect the actual anti-reflection. Therefore, this test examines the change in transmittance to confirm that the anti-reflection film has high penetration and good anti-reflection. The effect and the change in the transmittance of the antireflection film formed by the polymer film of different stacked layers (layer number calculation method such as test (A)) were examined. This test was carried out by the antireflection film obtained in the first embodiment (that is, the first charge polymer was PLD, the second charge polymer was PGA, and the substrate material was glass). Here, the antireflection film made of PLDs having different monomer repetition numbers and graft ratios was divided into three sub-test groups of D-1, D-2, and D-3, and the following were discussed.

(D-1) Permeability test of the polymer film prepared by PLD having monomer repeat number = 70 and graft ratio = 0.2

This sub-test measures the light transmittance of each group with an anti-reflection film made of a polymer film of 8 layers (D1 group) and 10 layers (D2 group), and is made of a glass substrate. As a control group (Group D0), the penetration map is shown in Figure 5. It can be seen from the figure that the transmittance of the anti-reflection film of the D1 group in the visible light range is higher than that of the control group, and the transmittance of the D2 group in the wavelength range of 450-800 nm is significantly higher than that of the control group. The formula of the transmittance (T%) = 1 - reflectance (R%) can be known that the transmittance is increased due to the decrease in reflectance, thereby confirming that the antireflection film of the present invention can indeed improve the antireflection film. The antireflection rate of the substrate.

(D-2) Permeability test of the polymer film prepared by PLD having monomer repeat number = 170 and graft ratio = 0.4

This sub-test measures the light transmittance of each group against an anti-reflection film made of a polymer film of 8 layers (D3 group) and 10 layers (D4 group), and is made of a glass substrate. As a control group (Group D0), the transmittance of 400 to 800 nm obtained from each group is shown in Fig. 6. It can be seen from the figure that the antireflection film of the group D3 of the present invention has a higher transmittance in the visible light range than the control group, and particularly compares the transmittance of 550 nm, and the antireflection film can reflect the transmittance from the original 92% of this (control group) increased to 98%, although the anti-reflection gain of the D4 group was not better than that of the D3 group, but the penetration rate was also clearly observed in the range of 550-800 nm compared with the control group. obviously increase.

(D-3) Permeability test of the polymer film prepared by PLD having monomer repeat number = 340 and graft ratio = 0.4

This sub-test is conducted on the anti-reflection film prepared by polymer film of 4 layers (D5 group) and 8 layers (D6 group), and the substrate is made of glass. The group (Group D0), the wavelength of 300 to 800 nm obtained by each group is shown in Figure 7. It can be seen from the figure that the antireflection film of the D5 and D6 groups of the present invention has higher transmittance in the visible light range than the control group, and in particular, the analysis of the D5 group can confirm that when the number of stacked layers of the polymer film is 4 layers, The antireflection film obtained by the precipitation of cerium oxide has remarkable anti-reflection performance, and as a result of the return-reflection test (A), it can be found that the anti-reflection is prepared from a polymer film having a thickness of about 20 to 30 nm. The film has good anti-reflection ability.

Please refer to Fig. 8 again to compare the transmittance of the anti-reflection film prepared by stacking 8 layers of polymer film, except for the D1, D3, and D6 groups and the D0 group. The penetration rate data of the D7 group and the D8 group were compared and analyzed for the penetration rate. The D7 group was an anti-reflection film made of a PLD having a monomer number of 170 and a graft ratio of 0.2. The D8 group is an antireflection film made of a PLD having a monomer repeat number of 340 and a graft ratio of 0.2. The transmittances of the D1, D3, D6 and D8 groups in the visible light range were larger than those of the control group, while the D7 group had a higher transmittance in the wavelength range of 530-800 nm than the D0 group.

In addition, the transmittance of the D1, D2, D3, D4, and D6 groups, the peak wavelength of the transmission spectrum, the reflectance, the thickness, the reflectance index, the roughness, and the porosity are also included. It is shown in Table 3 below. From the data of Table 3, it can be known that the transmittance of light on the anti-reflection film is substantially positively correlated with the porosity of the anti-reflection film.

Table 3: Test result data for each group

(E) Measurement of the transmittance of the antireflection film prepared by the second embodiment

This test compares the transmittance of the antireflection film (Group E1) and the control group (Group E0) obtained by stacking a polymer film having 5 layers, and the antireflection obtained in the second embodiment. The film was tested (ie, the first charge polymer was PLL-b-PS, the second charge polymer was PGA, and the substrate material was PMMA), and the results are shown in FIG. The test results show that the anti-reflection film of the second embodiment can also effectively enhance the anti-reflection effect of the substrate having the anti-reflection film.

Referring to FIG. 10 again, the right side of the substrate made of glass is passed through the preparation method of the anti-reflection film of the present invention, and the anti-reflection film is bonded to the right side surface of the substrate, and the left side of the substrate is not treated. The substrate can be clearly observed by the naked eye, and the substrate having the anti-reflection film greatly reduces the generation of reflected light, so that the text below the substrate is clearly visible.

In summary, the method for preparing the anti-reflection film of the present invention is performed on the surface of the substrate, and the polymer base film forming step, the polymer base film stacking step, and the repeating step are sequentially performed to form the polymer film. The surface of the substrate is then passed through the cerium oxide precipitation step to form the anti-reflective film. In view of the method for preparing the anti-reflection film of the present invention, the first charge polymer film and the second charge polymer film layer are alternately stacked in a solution process, and the steps are simple and need not be The invention can be carried out by using a large, precise, expensive and energy-consuming abutment. Compared with the vacuum coating method which is conventionally used for preparing an anti-reflection film, the present invention can greatly simplify the process of the anti-reflection film, thereby reducing the anti-reflection film. The cost of process costs.

Moreover, the method for preparing the antireflection film of the present invention processes the substrate by using the first charge polymer, the second charge polymer and the ceria precursor in a liquid state, so that the substrate can be formed in various shapes. The anti-reflection film is formed on the surface of the material to further increase the applicability of the anti-reflection film obtained.

While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.

Claims (10)

A method for preparing an anti-reflection film comprises: a substrate providing step of providing a substrate; and a polymer base film forming step of forming a first charge polymer film on the surface of the substrate by using a first charged polymer solution And forming a second charge polymer film on the surface of the first charge polymer film by using a second charge polymer solution, so that the first charge polymer film and the second charge polymer film together form a polymer a base film, wherein the first charge polymer solution comprises a first charge polymer and a first solvent, the second charge polymer solution comprises a second charge polymer and a second solvent, the substrate and the first The charge polymer has an opposite charge, and the first charge polymer and the second charge polymer have opposite charges; a polymer base film stacking step, the first charge polymer solution is applied to the second charge Forming another first charge polymer film on the surface of the polymer film, and forming a second charge polymer film on the surface of the other first charge polymer film by the second charge polymer solution to obtain the high score The base film surface is further stacked to form a polymer base film; in a repeated step, the polymer base film stacking step is repeated until a plurality of layers of the polymer base film form a polymer film on the surface of the substrate, and the polymer film is formed The thickness is at least 20 nm; and the cerium oxide precipitation step, the cerium oxide is precipitated in the polymer film with a cerium oxide precursor solution. The method for preparing an anti-reflection film according to the first aspect of the invention, further comprising a polymer film removing step of removing the polymer film after the ceria precipitation step. The method for producing an antireflection film according to claim 1 or 2, wherein the first charge polymer has an amine group, a mercapto group or an imidazole group, and the second charge polymer has a carboxyl group. a group, a phosphate group or a sulfate group. The method for producing an antireflection film according to the third aspect of the invention, wherein the first charge polymer is a polymer grafted with a hydrocarbon group, or the first charge polymer is a block polymer. . The method for preparing an anti-reflection film according to the fourth aspect of the invention, wherein the first charge polymer is polylysine grafted citric acid, and the graft ratio of the first charge polymer is 0.2 to 0.4. And the second charge polymer is poly-proline. The method for preparing an antireflection film according to claim 4, wherein the first charge polymer is polylysine-block-polystyrene, and the second charge polymer is polylysine . The method for preparing an antireflection film according to claim 5, wherein the first charge polymer solution has a pH of 4 to 7.5. The method for preparing an anti-reflection film according to claim 1 or 2, wherein the substrate is glass, polymethyl methacrylate, polycarbonate, indium tin oxide conductive glass, polyethylene terephthalate Alcohol ester or alumina. The method for preparing an anti-reflection film according to claim 1 or 2, wherein the cerium oxide precursor liquid system comprises a cerium oxide precursor, and the cerium oxide precursor is a tetraoxin group. a compound or a compound having a trioxane group. The method for producing an antireflection film according to the first or second aspect of the invention, wherein the antireflection film is obtained by an antireflection film having a thickness of 80 to 160 nm.