KR100579110B1 - Anti-reflection film composed with conducting polymer and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an antireflection film that prevents deterioration of image quality due to light reflection on various display screens such as CRT, liquid crystal display (LCD), plasma display (PDP), and the like. And a base film composed of a transparent polymer film 110, and at least one conductive layer 120 formed by stacking a conjugated polymer having a heterocycle structure on at least one surface of the base film. Therefore, the present invention has a high transparency, a thin thickness, excellent antistatic and electron shielding properties and thus can be widely used in the fields of electric, mechanical and electronics.

Description

Anti-reflection film composed with conducting polymer and manufacturing method

1 is a schematic view of an antireflection film formed by laminating a conductive polymer according to an embodiment of the present invention,

2 to 5 are schematic views showing different forms of the antireflective film, each of which is formed by stacking a conductive polymer according to the present invention;

6 is a block diagram showing a manufacturing process of the antireflection film according to the present invention shown in FIG.

7 is a block diagram showing a manufacturing process of the antireflection film according to the present invention shown in FIG.

  ♠ Explanation of symbols on the main parts of the drawing ♠

100: antireflection film 110: transparent polymer film

120: conductive layer 130: high refractive thin film layer

140: low refractive thin film layer 150: hard coating layer

The present invention relates to an antireflection film, and more particularly, to an antireflection film which prevents deterioration of image quality due to light reflection on various display screens such as CRT, liquid crystal display (LCD), plasma display (PDP) and the like. In addition, the present invention also relates to a method of manufacturing an antireflection film that prevents deterioration of image quality due to light reflection on various display screens.

In addition to the development of the battery and electronic industries and the advancement of the information and communication society, the demand for high definition and high definition is increasing in the electronic display field. The biggest problem of these electronic displays (CRT, LCD, PDP) is the deterioration of the image quality due to the reflection of light, another problem is that the contaminants such as dust easily adheres to the surface of the display or the monitor due to static electricity, and occurs in the display The electromagnetic waves may affect the human body and other indoor electronic devices. In order to secure these problems, conventionally, a plastic coating film having an anti-reflective function as well as an electrostatic / electromagnetic shielding function is directly attached onto a screen or embedded in a display.

In the related art, a theory of antireflective coating that dissipates reflected light reflected from a surface by stacking thin films having different refractive indices on the surface of an object has been known for a long time in the optical field. This theory has been difficult to apply to the actual product due to the absence of thin film forming technology, but since the 1940s vacuum deposition method, sputtering method has been applied in various ways.

A method of forming an anti-reflection layer on the plastic base material is ITO (Indium Tin Oxide - tin-doped indium oxide), TiO _2, a high refractive index inorganic material layers and low-refractive inorganic layers such as SiO _2, MgF _2, such as ZrO ₂ are alternately at least A method of laminating four or more layers by a vacuum deposition method or a sputtering method is known (US Pat. No. 5,744,227, US Pat. No. 5,783,049, Japanese Patent Application Laid-Open No. 5-307104, Japanese Patent Application Laid-Open No. 8-82701, and Japanese Patent Publication). Japanese Patent Application Laid-Open No. 9-197103, Japanese Patent Application Laid-Open No. 9-197102). The anti-reflection film manufactured by the vacuum deposition method or the sputtering method is excellent in the anti-reflection performance, but the process speed is about 1 m / min. There is also a problem to give. On the other hand, the method of forming an antireflection film by wet coating only a low refractive fluorinated polymer film (Japanese Patent Laid-Open Publication No. Hei 6-230201 and Japanese Patent Laid-Open Publication No. Hei 9-203801) is inferior in antireflection performance but the process speed is high to increase productivity. It is known that it can.

Low-reflective films designed with anti-reflective functions on transparent polymer films have been widely used in the electronics, electrical, and mechanical fields. In particular, when low-reflective films are used for displays such as CRTs, liquid crystal panels, and plasma displays, the reflectance of light is reduced It is known that a clearer image can be displayed.

In general, a low reflection film is formed of a transparent polymer resin film such as a polyester film, a triacetate cellulose film, or a polycarbonate film by sputtering or depositing inorganic oxides such as SiO ₂ , TiO ₂ , and ITO (Indium Tin Oxide). It has been produced by forming a multilayer thin film of at least four layers or by forming a antireflection film (low reflection or antireflection film) by wet coating a compound containing fluorine.

However, when manufacturing a multilayer anti-reflection film by the method of sputtering or vapor deposition, there is no problem of deterioration of transparency or opticality such as coloration, but processing cost increases and it causes a large increase in manufacturing cost. When the antireflection layer is formed only of SiO ₂ , TiO _2, or the like, the antireflection layer does not have an antistatic function, so that the surface is contaminated due to exposure to static electricity, and dust or the like is easily attached. Whether an inorganic oxide ITO layer was separately formed or an antistatic agent was added as a separate layer, an antistatic layer was formed on the surface layer to prevent static electricity.

Recently, with the rapid growth of the flat panel display industry and the spread of anti-reflective films, the discovery of new materials for cost reduction has emerged as an important research project.

The transparent conductive layer used in the display film is generally used indium tin oxide (ITO), which is an inorganic oxide in general, but the price is expensive, and various efforts have recently been made to replace it. A typical example is to make an antistatic layer of a conductive material by a wet coating method, in which case it is difficult to control the thickness of the film, the transparency is lowered, the coloring is likely to occur, and the antistatic agent penetrates to the surface. There are known problems.

Meanwhile, recently, conductive polymers having heterocycles such as polypyrrole and polythiophene are relatively easy to synthesize, have high electrical conductivity, and are known as new materials having stable physical properties in the air. There is a lot going on.

As a method of synthesizing a conductive polymer, chemical oxidative polymerization, electro-chemical polymerization, and the like are known. However, since the conductive polymer is difficult to be processed into a film form because it is not melted or dissolved, the polymer synthesized by the chemical oxidation method is difficult to form a thin film because it is manufactured in the form of particles, and synthesized by an electrochemical polymerization method. Polymers are difficult to form in a thin film form and the mechanical strength is low because of many limitations in practical applications.

In recent years, as a method of complementing such a problem, a method of providing an antistatic function by mixing a conductive polymer in the form of a particle with a general polymer to form a composite material having enhanced workability and physical properties and coating the substrate film is provided. However, in order to provide sufficient adhesion, a large amount of mixed resin is required, which has a problem of greatly reducing the properties of the conductive polymer. In addition, even if the composite material is coated on a polymer resin film to impart an antistatic function, the thickness of the coating layer is thick to about several microns, so that the transparency is poor and there is a limit to use as a multilayer thin film to control fine thickness. There is a difficulty in going through several stages of processing before winning the prize.

The present inventors have tried to solve the problems such as the physical properties of the existing anti-reflection film and the complexity of the manufacturing process, as a result of the conjugated polymer having a heterocycle structure on the surface of the transparent polymer substrate film The present invention was completed by studying a laminating method and manufacturing a new material having a new function of controlling the refractive index as well as the conductive layer of the optical low reflection film.

Accordingly, an object of the present invention is to provide an antireflection film having an antistatic function and a low reflection function at the same time, and a method of manufacturing the same, by forming a conductive polymer layer having a high transparency and a thin thin film form that can be controlled to a nano level. .

The anti-reflection film of the present invention for achieving the above object is formed by laminating a conjugate film of a heterocycle-based structure of Formula 1 below on a substrate film consisting of a transparent polymer film, and at least one side of the substrate film At least one conductive layer is included.

In addition, the anti-reflection film manufacturing method of the present invention, the step of applying an oxidizing agent to at least one surface of the base film composed of a transparent polymer film, and the heterocycle-based structure of the formula (1) to the base film And forming at least one conductive layer from the conjugated polymer of the heterocycle-based structure of Chemical Formula 1, which is formed by washing and removing an unreacted oxidant after a gas phase polymerization reaction of a conjugated monomer.

In the following, with reference to the accompanying drawings a preferred embodiment of the antireflection film and a method for manufacturing the conductive polymer laminated according to the present invention will be described in detail.

1 is a schematic view of an antireflection film formed by stacking a conductive polymer according to an embodiment of the present invention. As shown in FIG. 1, the antireflection film 100 of the present invention has a transparent polymer film 110 as a base film, and is a conjugated polymer having a heterocycle structure manufactured on the surface of the base film by vapor phase polymerization. By forming a conductive polymer layer 120 (hereinafter referred to as "conductive layer") formed by laminating, the thickness is thin, and has excellent antistatic property and electron shielding property.

The transparent polymer film 110 used as the base film in the present invention is a substrate film that has been commonly used, for example, a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene Film, cellophane, diacetylcellulose film, triacetate cellulose film, acetylcellulose butyrate film, polyvinyl chloride film, polyvinyl alcohol film, polystyrene film, polyethylene-acetic acid film, polyvinylidene chloride film, polycarbonate film, polyacryl Films, polymethylpentene films, polysulfone films, polyamide films and the like can be used. The higher the transparency, the better the transparent polymer film is, and the visible light transmittance is preferably about 75 to 92%. That is, the transparent polymer film used for the production of low reflection film should generally have a visible light transmittance of 75 to 92%. In addition, the thickness of the transparent polymer film is preferably 10 to 1000 µm, more preferably 20 to 200 µm.

In the present invention, the polymer used to form the conductive layer is a conjugated system having a heterocycle structure, and specifically, a heterocycle conjugated system including oxygen (O), selenium (Se), nitrogen (N) or sulfur (S) atoms. It is a polymer. More preferably, as the conjugated polymer of the heterocycle-based structure used in the present invention, pyrrole, thiophene, furan, serenophene and derivatives thereof may be used as represented by the following Chemical Formula 1.

In Formula 1, X is O, Se, S or NH, and R ₁ and R ₂ are H, C ₃ to C ₁₅ alkyl group, C ₃ to C ₁₅ alkyl ether, halogen atom or hydrocarbon together with S, O It is a substituent of a structure containing at least one atom, such as and forming a cycle structure, and in some cases, may include a functional group including its own doping function.

In the present invention, by generating a conjugated vapor (monomer) vapor of the heterocycle structure of the general formula (1) to directly induce the gas phase polymerization on the surface of the transparent polymer substrate film to form a conductive layer at the same time polymerization to produce an antireflection film Although not limited to this. That is, the anti-reflection film 100 according to the present invention comprises the conductive layer 120 formed by stacking a conjugated polymer of a heterocycle-based structure of Formula 1 on at least one surface of the transparent polymer film 110. By constructing at least one layer, the antistatic and low reflection functions can be sufficiently obtained simultaneously.

As described above, the antireflection film of the present invention has a conductive layer having a thickness of 10 to 1000 nm, a visible light transmittance of 60 to 99%, a sheet resistance of 10 ² to 10 ⁹ GPa / square, and a refractive index of 1.0 to It has a characteristic of 1.54. This property evaluation was obtained through <Measurement of Properties>, which will be described below.

The present invention may have a more preferable form than the form as described above, the preferred form, as shown in Figure 2, the conductive layer 120 between the transparent polymer film 110 and the conductive layer 120 By forming the high refractive thin film layer 130 having a higher refractive index, a more improved low reflection function can be obtained. In this case, the high refractive thin film layer 130 is formed of a polymer compound or TiO ₂ having a higher refractive index than the conductive layer 120. In addition, the present invention is a low refractive index having a lower refractive index than the conductive layer 120 on top of the conductive layer 120 laminated on at least one upper surface of the transparent polymer film 110, as shown in FIG. By forming the thin film layer 140, a further improved low reflection function can be obtained. In this case, the low refractive thin film layer 140 may be a fluorine-based polymer compound or SiO ₂ having a lower refractive index than the conductive layer 120 may be used. 2 and 3 are schematic views showing different forms of the antireflection film formed by stacking the conductive polymer according to the present invention, respectively.

In addition, as shown in Figure 4, the anti-reflection film 100 of the present invention is a hard coating layer 150 as needed between the high refractive thin film layer 130 and the transparent polymer film 110 laminated as shown in FIG. It may be formed. The hard coating layer 150 serves to prevent surface scratches by improving the surface strength of the transparent polymer film 110. At this time, the hard coating layer 150 is generally preferably used a thermosetting or UV curing acrylic resin. In addition, as shown in FIG. 5, the antireflection film 100 of the present invention may form the low refractive thin film layer 140 on the conductive layer 120 stacked as shown in FIG. 4. 4 and 5 are each a schematic view showing another form of the antireflection film formed by stacking the conductive polymer according to the present invention.

The high refractive thin film layer 130, the low refractive thin film layer 140 and the hard coating layer 150 is formed through a known method well known in the art.

On the other hand, the present invention includes a method for producing an anti-reflection film, below will be described with a specific example of a multi-layered film composed of a conductive layer and another functional layer on the polymer substrate film.

FIG. 6 is a block diagram illustrating a manufacturing process of the antireflection film according to the present invention shown in FIG. 2. As shown in FIG. 2 and FIG. 6, first, a solution having a higher refractive index than the polymer of Formula 1 is coated on the transparent polymer film 110 and then dried to form a high refractive thin film layer 130 (S11). Then, by applying an oxidizing agent on the upper surface of the high refractive thin film layer 130, and then to the conjugated polymer of the formula (1) formed by washing and removing the unreacted oxidant after the gas phase polymerization reaction (monomer) of the formula (1) The conductive layer 120 is formed (S12).

In the present invention, in forming a conductive layer on a base film or a functional thin film layer, the above gas phase polymerization method may be used, and as an oxidizing agent, Lewis acids such as Cu (ClO ₄ ) · 6H ₂ O and FeCl ₃ may be used. The oxidizing agent is used after being dissolved in a solvent containing one or two or more selected from polar organic solvents, preferably alcohols. In addition, the oxidizing agent may be a polymer such as polyurethane, polyvinyl chloride, polyvinyl alcohol, methyl cellulose, and chitosan, as necessary, within the range of 1 to 20 parts by weight (based on solids content) based on 1 part by weight of the oxidizing agent as a binder resin. It can be contained. When the polymer is added in an amount less than 1 part by weight, the function as a binder is lost, and when added in an amount exceeding 20 parts by weight, there is a problem of lowering conductivity. The polymer added to the oxidizing agent has a high affinity for the conjugated monomer of the heterocycle-based structure depending on the content thereof, and thus is suitable as a host polymer during gas phase polymerization for forming a conductive layer. However, when the host polymer is used, the physical properties of the conductive polymer material itself may be reduced. In particular, there may be a problem that it is difficult to control the refractive index.

Then, a coating liquid containing a fluorine substituent having a function of preventing contamination on the conductive layer 120 as needed to have a thickness of 1 micron or less to have a three-layer structure. Here, the coating layer (not shown) containing a fluorine substituent having an antifouling function preferably has a lower refractive index than the conductive layer 120. By forming the coating layer, the antireflection performance is further improved. It may be (S13).

As the gas phase polymerization method for forming the conductive layer, a method of distilling a monomer in a closed chamber at a temperature range of 10 to 100 ° C., and a chemical vapor deposition (CVD) method may be used. The conductive layer by the vapor phase polymerization method can be controlled in the thickness range of 10 to 1000 nm. That is, there is a current technical difficulty in manufacturing the conductive layer of the present invention to less than 10 nm, when the thickness exceeds 1000 nm, the desired effect can not be obtained in the present invention. When the gas phase polymerization is completed, the film is washed with alcohols, water and the like to remove unreacted impurities. However, the thin film formation method itself of the conductive layer by the present gas phase polymerization method is not limited by the present invention.

7 is a block diagram showing a manufacturing process of the antireflection film according to the present invention shown in FIG. 3 and 7, first, the conductive layer 120 is formed by laminating the polymer of Chemical Formula 1 by vapor phase polymerization on the transparent polymer film 110 (S21). In this case, the conductive layer 120 is formed using the same method and oxidizing agent and / or host polymer as described above. Then, after coating a solution having a lower refractive index than the conductive layer 120 and dried to form a low refractive thin film layer 140 (S22), if necessary, the fluorine substituent having a pollution prevention function in the same manner as described above To form a coating layer containing (S23).

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

<Example 1>

First, an oxidizer solution was prepared by dissolving iron trichloride (FeCl ₃ ) at a concentration of 2% by weight in a methyl alcohol solvent. Then, the prepared oxidant solution was spin-coated on a 188 μm thick polyethylene terephthalate film (PET) and dried at about 65 ° C. for 3 minutes. The light yellow polyester film coated with the oxidizing agent was kept at 60 ° C. (30 seconds) reaction condition in the CVD chamber where thiophene monomer production was induced, and then washed with methanol solvent for the purpose of removing unreacted materials. A transparent light blue conductive polythiophene film was prepared by the above method, and the physical properties of the antireflective film of the present invention were shown in Table 1 below.

<Example 2-4>

Prepared by the same composition and method as in Example 1, but the reaction conditions in the CVD chamber were carried out differently at 30 ℃ (30 seconds), 45 ℃ (30 seconds), 55 ℃ (5 minutes), respectively, the reflection of the present invention The prevention film was prepared. Physical properties of the anti-reflection film of the present invention prepared above are shown in Table 1 below.

<Measurement of physical properties>

The physical properties of the antireflection film of the present invention prepared above were measured by the following test method.

1) Coating layer thickness: measured by electron microscope

2) Permeability: measured with HP 8453 UV / VIS spectrophotometer (ASTM D 1003).

3) Sheet resistance: measured with DINS four-point probe MP MCP-T 350 (ASTM D 257).

4) Hardness: measured with a pencil hardness tester (ASTM D 3363-92a).

5) Reflectance: Measured at 5 ^o using a Shimadzu MPC-3100 instrument.

6) Film adhesion: measured with a cross hatch cutter (ASTM D 3359).

7) Thermal stability: TGA 2050 analyzer (Tupon) measured at a heating rate of 10 ° C / min in the range of 30 to 500 ° C.

division Coating layer thickness (nm) Visible light transmittance (%) Sheet resistance (Ω / square) Reflectance (%) Film adhesion Thermal stability PET film - 88 10 ¹⁶ 10 - - Example 1 52 83 10 ⁴ 7 Great stability Example 2 24 89 10 ⁶ 8 Great stability Example 3 32 85 10 ⁵ 8 Great stability Example 4 90 80 4000 6 Great stability

As shown in Table 1, the antireflection film used in the displays of Examples 1 to 4 according to the present invention had a significant decrease in reflectance and sheet resistance compared to the PET film as the base film. In addition, Example 1 [60 ℃ (30 seconds)], Example 2 [30 ℃ (30 seconds), the physical properties of Example 4, which was carried out at 55 ℃ for 5 minutes to produce an anti-reflection film only gave a change in temperature and time ), As compared with Example 3 [45 [deg.] C. (30 sec)], the numerical value was lowered, indicating that an appropriate reaction temperature and time influenced the film produced.

Example 5

First, an oxidizer solution was prepared by dissolving iron trichloride (FeCl ₃ ) in a 3% by weight concentration in a methyl alcohol solvent. Then, the oxidant solution prepared above was spin coated on a corona treated 0.1 mm thick Aton film (JSR) and dried at about 65 ° C. for 5 minutes. The oxidant-coated aton film was allowed to remain at 60 ° C. (30 sec) reaction conditions in a CVD chamber in which thiophene monomer production was induced, and then washed with methanol solvent for the purpose of removing unreacted materials. The conductive polythiophene film was prepared by the above method, and the physical properties of the antireflective film of the present invention were measured by the <physical measuring method> and are shown in Table 2 below.

division Coating layer thickness (nm) Visible light transmittance (%) Sheet resistance (Ω / square) Reflectance (%) Film adhesion Thermal stability Aton film - 92 10 ¹⁶ 7 - - Example 5 48 88 5 x 10 ⁵ 3.5 Great stability

As shown in Table 2, the antireflection film (Example 5) of the present invention prepared using a corona treated aton film as the base film exhibits excellent characteristics as a conductive film as compared to the base film.

<Example 6-9>

Manufactured in the same manner as in Example 1 except using a pyrrole monomer, a thiophene monomer, a furan monomer, and a serenophene monomer as a heterocycle conjugated monomer constituting a conductive layer, a reaction temperature of 40 ° C. (1 minute) The anti-reflection film of the present invention was prepared by carrying out. Physical properties of the anti-reflection film of the present invention prepared by the <physical measuring method> is shown in Table 3 below.

division Conductive layer Coating layer thickness (nm) Visible light transmittance (%) Sheet resistance (Ω / square) Reflectance (%) Film adhesion Thermal stability Example 6 Polypyrrole 80 75 5 x 10 ⁴ 11 Great stability Example 7 Polythiophene 50 86 3 x 10 ³ 8 Great stability Example 8 Poly Furan 45 81 8 x 10 ⁸ 11 Great stability Example 9 Poly serenophene 60 80 7 x 10 ⁹ 11 Great stability

Table 3 shows the physical properties of the anti-reflection film of the present invention prepared according to the type of heterocyclic conjugated monomer, the anti-reflection film is 45 ~ 80 nm thickness of the conductive layer, 75 ~ visible light transmittance The sheet resistance was 86%, the sheet resistance was 7x10 ⁹ to 3x10 ³ Ω / square, and the polythiophene showed an excellent effect with a reflectance of 8%. Particularly, the polythiophene of Example 7 showed a high effect.

As described in detail above, the antireflection film of the present invention has high transparency, a thin thickness, and excellent antistatic and electron shielding properties, and thus can be widely used in the fields of electric, mechanical, and electronic.

In addition, the production method of the present invention can be a series of processes from the polymerization to the production of the film has the effect of low manufacturing cost.

In the above description, the technical details of the antireflection film and the manufacturing method of the conductive polymer laminated by the present invention have been described together with the accompanying drawings, which illustrate the best embodiment of the present invention by way of example and not limit the present invention. .

In addition, it is obvious that any person skilled in the art can make various modifications and imitations within the scope of the appended claims without departing from the scope of the technical idea of the present invention.

Claims (8)

A base film composed of a transparent polymer film, Antireflection film comprising a conductive polymer laminated on at least one side of the base film comprising at least one conductive layer formed by laminating a conjugated polymer of the heterocycle-based structure of formula (1) below. Formula 1

In Formula 1, X is O, Se, S or NH, and R ₁ and R ₂ are H, C ₃ to C ₁₅ alkyl group, C ₃ to C ₁₅ alkyl ether, halogen atom or hydrocarbon together with S, O It is a substituent of the structure containing at least 1 or more atoms, etc., and forming a cycle structure. The antireflection film of claim 1, further comprising a high refractive index thin film layer formed of a polymer compound having a higher refractive index or Ti0 ₂ than the conductive layer between the base film and the conductive layer. . The antireflection film according to claim 2, wherein a hard coating layer is further formed between the base film and the high refractive thin film layer to improve the surface strength of the base film. The reflective structure of claim 1 or 3, further comprising a low refractive index thin film layer formed of a fluorine-based polymer compound or Si0 ₂ having a lower refractive index than the conductive layer on the conductive layer. Prevention film. The first step of applying an oxidizing agent to at least one surface of the base film composed of a transparent polymer film, the gas phase polymerization reaction of the conjugated monomer (monomer) of the heterocycle structure of the formula (1) to the base film to which the oxidant is applied After the anti-reacted oxidizing agent formed by washing and removing the anti-reflection film consisting of a conductive polymer laminated, characterized in that it comprises a second step of forming at least one conductive layer with a conjugated polymer of the heterocycle structure of formula (1) Manufacturing method. Formula 1

In Formula 1, X is O, Se, S or NH, and R ₁ and R ₂ are H, C ₃ to C ₁₅ alkyl group, C ₃ to C ₁₅ alkyl ether, halogen atom or hydrocarbon together with S, O It is a substituent of the structure containing at least 1 or more atoms, etc., and forming a cycle structure. The antireflection film according to claim 5, further comprising a high refractive index thin film layer formed of a polymer compound having a higher refractive index or Ti0 ₂ than the conductive layer on the base film before the first step. Manufacturing method. The antireflection of claim 5, further comprising forming a low refractive thin film layer of Si0 ₂ or a fluorine-based polymer compound having a lower refractive index than the conductive layer after the second step. Method for producing a film. The method of manufacturing an antireflection film according to any one of claims 5 to 7, wherein a host polymer is further added to the oxidant.

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