KR20170036166A

KR20170036166A - Method for producing film coating agent having anti-finger treatemtn and anti-reflection

Info

Publication number: KR20170036166A
Application number: KR1020150134575A
Authority: KR
Inventors: 김영준; 조석형
Original assignee: 청운대학교산학협력단; 주식회사 가남
Priority date: 2015-09-23
Filing date: 2015-09-23
Publication date: 2017-04-03
Also published as: KR101764581B1

Abstract

The present invention relates to a coating agent having excellent properties such as anti-reflective properties, fingerprint resistance and scratch resistance by preparing inorganic nanoparticles which are ultrafine particles and hybridizing organic materials such as monomers and organosilanes with organic materials.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for manufacturing a coating film for an inner fingerprint and an inner reflection film,

TECHNICAL FIELD The present invention relates to a coating agent having superior properties such as anti-reflective properties, fingerprint resistance and scratch resistance by preparing inorganic nanoparticles which are ultrafine particles and hybridizing organic materials with monomers and organic silanes.

Display Functional Coating is an antireflection coating that prevents deterioration of image quality due to high hardness and light reflection on the screen as display devices such as LCD and OLED are enlarged and advanced, Super water repellent or inner fingerprint coating. In particular, mobile devices such as mobile phones and tablet PCs are emerging as main products, and demand for such scratches, fingerprints, and reflection prevention is increasing in display windows.

The anti-reflection, anti-fingerprint and scratch characteristics have been pointed out as a problem to be solved in the optical lens market for several decades. Nowadays, the characteristics required for optical lenses are applied to windows of mobile displays, High durability is required due to the nature of the products that the hands come into contact with from time to time. Window manufacturers are addressing the scratch resistance problem by developing window-integrated, especially tempered glass, integrated touch devices for the launch of touch-type display devices. Mobile vendors are working on optical lenses It also utilizes the technology of the multi-layer structure used. Anti-Refraction coating technology is a technique to minimize reflection of light and maximize transparency by coating with a single substance or multilayer structure with controlled refractive index (Refractive Index) to minimize glare by minimizing reflection .

At present, antireflection technology is a standard structure formation using a difference in refractive index by a multilayer film structure, and it mainly uses an electron beam method to deposit different materials having different refractive indexes in multiple layers, However, in the case of a display based on a touch method, contact with a human hand is frequent, resulting in poor durability. In order to overcome such disadvantages, it is necessary to hybridize the organic material to improve the durability of the inorganic material and to combine the functionality of the organic material and to apply the material having low surface energy. If oil-repellent, it should exhibit excellent fingerprint characteristics with oil-repellent oil.

In order to provide the fingerprint and anti-reflection function, it is required to implement nanostructures. If considering future products, technological complementary measures that can be applied to flexible glass are needed. For this purpose, nanostructures of polymers and inorganic materials are manufactured It is required to have a capability of being applied not only to scratch resistance and fingerprint but also to glass and polymer films.

Korea is leading the global market for semiconductors and display related products, but the world's functional film manufacturing technology is owned by the United States and Japan. In order to solve this imbalance, participation and investment of Korean companies in order to eradicate the functional film market is becoming more and more active, and competition among domestic and foreign companies is becoming more and more intense. In addition, the proportion of the material cost of the products is high, and demand for price cuts by consumers is increasing.

Representative companies related to foreign functional film are developing computer monitor and LCD display security film with 3M, and have excellent performance in resolution and transparency. And ITO film related companies are Nitto Denko, Toray, Oike, Suzutora and Toppan. Domestic functional coating companies include Woosin Industries and Baekos. Functional film makers include Sehwa P & C, Korea Engineering, Fox Gill and Pure Mate. ITO film companies are 3 or 4 such as Digitech System and SKC Haas, all of which are known to produce coatings in foreign countries through technical cooperation.

Hereinafter, the state of technology related to the present invention will be described.

Display-related functional films account for about 73% of the total functional film market, which is superior to semiconductor / substrate functional films (12.8%) and energy related films (6.8%). In particular, the market for functional films for display in Japan is expected to grow at a CAGR of 6.4% from about 1.9 trillion yen in 2011 to about 2.44 million yen by 2015. The domestic market is expected to grow at a CAGR of 6.4% from 6.7 trillion won in 2011 to 8.6 trillion won by 2015.

In general, an antireflection film (AR film) has been applied to a polarizing plate of a liquid crystal display device or an optical filter of a plasma display panel (PDP) to reduce reflection of external light to improve the sharpness and visibility of an image 2003-149413, Korean Patent Publication No. 2003-0066178). BACKGROUND ART [0002] The theory of anti-reflective coatings which have long been known to form thin films having different refractive indices on the surface of an object to thereby eliminate the reflected light reflected from the surface has been known in the optical field. However, this theory has been difficult to put into practical use due to the lack of thin film forming technology. Since the 1940s, various techniques have been applied to real life as well as development of dry thin film forming technique by vacuum deposition method and sputtering method. Demand for anti-reflective coatings has been greatly increased with development and upgrading.

Reflected light reflected from the surface of the optical product causes the following major problems. First, the ratio of the reflected light reflected from the surface of the substrate to the incident light is lowest with respect to the normal incident light (incident angle of 0 DEG in the normal), and increases as the angle of the incident light increases. In the case of a flat panel display such as a plasma display panel (PDP) or a plasma display panel, the resolution of the image is significantly reduced due to the difference in the reflection ratio, and the image is totally blurred according to the viewing angle. Second, the increase of the reflected light deteriorates the transmittance of the substrate, which causes problems in products requiring high transmittance such as glasses and optical lenses. In the case of an optical substrate on which such a reflected light is amplified as in the case of a compound lens or the like, such a problem of reduction in transmittance may be very serious. Third, unnecessary gloss appears on the surface of the optical substrate due to reflected light. In order to solve these problems, anti-reflective coatings have recently been widely applied to optical substrates and display products.

Korean Patent Laid-Open Publication No. 2003-0057335 discloses a light guide plate of a backlight unit in which an antireflection layer composed of a concave portion and a convex portion is formed on an outgoing surface of a light guide plate to achieve a high transmittance through an excellent antireflection effect, Is proposed. Such an antireflection layer reduces the reflectance at the surface by forming fine irregularities such as a micro-pattern on the surface of the optical substrate without using the high refractive index layer and the low refractive layer of the thin film. If the micropattern can not be precisely formed due to the limitations of the process, scattering of the visible light or scattering of the visible light to the upper side of the light guide plate, which can lower the brightness of the liquid crystal display device, There is a possibility that the light may become an obstacle in the progress of the light.

Japanese Laid-Open Patent Publication No. 2003-149413 discloses a liquid crystal display device having a wide viewing angle and an antireflection function that does not cause a decrease in contrast, a gradation or a black inversion and a color change due to a change in viewing angle. In order to realize this, a polarizing plate in which a light diffusion layer composed of a light transmitting resin and transparent fine particles (scattering body) containing a high refractive index monomer or inorganic particles is formed on a cellulose acetate film and a low refractive index layer is formed on the light diffusion layer Is applied to the viewing side (on the basis of the liquid crystal cell) of the liquid crystal display device. Refractive index layer having a refractive index of 1.35 to 1.45, which is a crosslinked cured product by thermal or ionizing radiation, of a composition containing a fluorine-containing compound and inorganic fine particles in order to impart an antireflection function of external light to a polarizing plate on the viewer side, An anti-glare film composed of a light-transmitting resin having a refractive index of 1.64 to 1.8 and a light-diffusing layer composed of light-transmitting fine particles (scattering body). However, this antiglare film is an antiglare film for a polarizing plate which can not be used for a backlight unit of a liquid crystal display device.

Japanese Patent Application Laid-Open No. 2003-149413, Korean Patent Publication No. 2003-0066178 Korean Patent Publication No. 2003-0057335

The present invention aims to provide a coating agent having excellent properties such as anti-reflective properties, fingerprint resistance and scratch resistance by preparing inorganic nanoparticles which are ultrafine particles and hybridizing a organic material with monomers such as organic and organic silane, .

In order to achieve the above object,

The present invention relates to a process for preparing a mixed solution by mixing acetone, distilled water and TEA (triethylamine), adding MTMS (methyl trimethoxy silane) or methacryloyl aminopropyltri methoxy silane (MTMS) to the mixed solution for 20 to 30 hours, (S10) of preparing a nanoparticle solution,

The functional particle solution prepared in step S10, MTMS, Trifluoropropyltrimethoxysilane (TFPTMS), nitric acid, IPA and distilled water are added and reacted for 20 to 30 hours to prepare a solution of a fingerprint / (S20). &Lt; / RTI >

The scratch resistant, fingerprint proof and antireflection functional coating material according to the present invention has the following effects.

first. In addition to mobile phones and tablet PCs, it can also be applied to TVs, game machines, PMPs, MP3 players, LCD TVs, and protection windows for PV modules that are seeking interactive services.

second. Unlike nanocomposite materials, nanohybrid materials have little increase in viscosity even when a high content of ceramics is added (dissolved), making them easy to manufacture and form, making them applicable to advanced functional materials.

third. It is excellent in electrical, mechanical and optical properties, and can be used as a hard coating material for various films (optical film, dough film), a corrosion preventing and abrasion resistance of a wear-resistant coating material and a metal foil on the surface of a plastic molding, / Insulation varnish of metal coil for transformer.

fourth. In particular, when heat resistant resin is applied, it is excellent in heat resistance, high thermal conductivity and chemical stability, and can be used for electric parts of electric vehicles, printed electronic devices (TFT, RFID), highly integrated semiconductors, flexible displays (OLED, electronic paper) It can be used as a core part material such as a light source and a film battery or as a sealing material.

fifth. It is possible to utilize all the fine devices and parts manufactured through the wet printing process, which have recently been highlighted, as materials for electrical insulation, substrates, and protective packages.

Sixth. It contributes to the performance and reliability of high-voltage motors, transformers, generators, and large-scale heat-transfer equipment, where high-voltage power materials with high voltage and current are used.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a process of manufacturing an inner fingerprint / inner reflection film coating according to the present invention; FIG.

As shown in FIG. 1, the method for manufacturing an inner fingerprint / inner reflection film coating according to the present invention comprises preparing a mixed solution by mixing acetone, distilled water and TEA (triethylamine), adding MTMS (methyl trimethoxy silane) , Adding MAPTMS (Methacryloyl aminopropyltri methoxy silane) for 20 to 30 hours to prepare a functional nanoparticle solution (S10)

The functional particle solution prepared in step S10, MTMS, Trifluoropropyltrimethoxysilane (TFPTMS), nitric acid, IPA and distilled water are added and reacted for 20 to 30 hours to prepare a solution of a fingerprint / Step S20.

·

At this time, the functional nanoparticle solution is prepared by mixing 80 wt% to 97 wt% of acetone, 2 wt% to 15 wt% of distilled water, and 0.1 wt% to 5 wt% of TEA (triethylamine)

5 to 30 wt% of MTMS (methyl trimethoxy silane) and 1 to 7 wt% of methacryloyl aminopropyltri methoxy silane (MAPTMS) are added to 69 to 90 wt% of the mixed solution, and the mixture is reacted for 20 to 30 hours.

When the amount of acetone used is less than 80 wt%, the homogeneous composition of the mixed solution is difficult. When the amount of acetone is more than 97 wt%, the content of the other components is decreased, , Problems may occur in preparing the antireflective coating solution. Therefore, the amount of acetone used is preferably limited to a range of 80 to 97 wt% with respect to the total weight of the mixed solution.

The alkoxy reaction in which the amount of distilled water used is less than 2 wt% does not occur in the composition of the mixed solution, and when it exceeds 15 wt%, there is a problem of precipitation. Therefore, the use amount of the distilled water is 2 to 15 wt %. &Lt; / RTI >

In the composition of the mixed solution, there is a problem that the reactivity of TEA (triethylamine) is less than 0.1 wt%, and when it exceeds 5 wt%, there is a problem of odor and excessive reaction. The amount to be used is preferably limited to a range of 0.1 to 5 wt% with respect to the total weight of the mixed solution.

The mixed solution prepared through the above process is reacted with MTMS (methyl trimethoxy silane) and MAPTMS (methacryloyl aminopropyltri methoxy silane) to prepare a functional nanoparticle solution.

In this case, the amount of the mixed solution used is 69 to 90 wt%. When the amount of the mixed solution is less than 69 wt%, it is not economical. When the amount of the mixed solution exceeds 90 wt% Is preferably limited to a range of 69 to 90 wt% with respect to the total weight of the solution.

The use amount of the MTMS (methyl trimethoxy silane) is 5 to 30 wt%. When the amount of the MTMS is less than 5 wt%, the hydrophobic property is deteriorated. When the amount is more than 30 wt%, the MTMS methyl trimethoxy silane) is preferably limited to a range of 5 to 30 wt% based on the total weight of the functional nanoparticle solution.

When the amount of the methacryloyl aminopropyltri methoxy silane (MAPTMS) is less than 1 wt%, the amount of the vinyl group is too small to have a low crosslinking ability. When the amount of the vinyl monomer exceeds 7 wt% The amount of MAPTMS to be used is preferably limited to a range of 1 to 7 wt% based on the total weight of the functional nanoparticle solution.

A specific example of the composition of the mixed solution is the same as in Example 1 below.

The mixture solution was mixed with 240 ml of acetone, 16 ml of distilled water and 4 ml of TEA (triethylamine), and 50 g of MTMS (methyl trimethoxy silane) and 10 g of MAPTMS (Methacryloyl amonopropyltri methoxy silane) To prepare a mixed solution.

The functional nanoparticle solution prepared through the above steps is prepared by mixing the composition of the functional nanoparticle solution with MTMS, Trifluoropropyltrimethoxysilane (TFPTMS), nitric acid, IPA and distilled water.

More particularly, the present invention relates to a process for producing a functional nanoparticle solution, which comprises: 2 to 15 wt% of a functional nanoparticle solution; 55 to 75 wt% of MTMS; 8 to 20 wt% of Trifluoropropyltrimethoxysilane (TFPTMS), 0.1 to 5 wt% of nitric acid, 6 wt% for 20 to 30 hours to prepare an anti-fingerprint anti-reflective coating solution according to the present invention.

When the amount of the functional nanoparticle solution used is less than 2 wt%, the antireflection performance is poor. When the amount exceeds 15 wt%, the light permeability is inferior. Therefore, It is preferable to limit the amount to 2 to 15 wt% with respect to the total weight of the antireflection coating solution.

When the amount of the MTMS used is less than 55 wt%, the hydrophobicity is poor. When the amount of the MTMS is more than 75 wt%, there is a problem of showing excessive hydrophobicity. Therefore, Is preferably limited to a range of 55 to 75 wt%.

If the amount of the hydrofluoric acid silane used is less than 8 wt%, the hydrophobicity of the solution is deteriorated. If the amount of the hydrofluoric acid silane exceeds 20 wt% Is preferably limited to a range of 8 to 20 wt%.

When the amount of the nitric acid used is less than 0.1 wt%, the catalyst serves as a problem. On the other hand, when the amount of the nitric acid exceeds 5 wt%, there is a problem of acid smell. But is preferably limited to a range of 0.1 to 5 wt% with respect to the total weight.

If the amount of IPA used is less than 8 wt%, there is a problem of precipitation of reactants. When the amount of IPA is more than 20 wt%, there is a problem in economy. Therefore, the amount of IPA used is preferably But is preferably limited to a range of 8 to 20 wt%.

When the amount of the distilled water is less than 0.1 wt%, the reaction does not occur. When the amount of the distilled water exceeds 6 wt%, there is a problem that excessive reaction occurs. Therefore, To be in a range of 0.1 to 6 wt% based on the total weight of the composition.

A specific example of the composition of the above-mentioned fingerprint / anti-reflection coating solution is the same as in Example 2 below.

50 g of the functional nanoparticle solution, 500 g of MTMS, 100 g of Trifluoropropyltrimethoxysilane (TFPTMS), 10 mL of nitric acid, 100 g of IPA and 16 g of distilled water are reacted for 20 to 30 hours to prepare a fingerprint and anti-reflection coating solution.

The evaluation of the inner fingerprint and anti-reflective coating solution (coating film) manufactured through such a manufacturing process will be described below.

A section of a 29 mm diameter silicone rubber is coated on an acrylic plate with a film thickness of 0.5 mm by using artificial fingers using a coating film Cw specified in JIS R6252, abrasive A and abrasive paper having a particle diameter P240, and quantitative adhesion test is performed using oleic acid. Apply artificial hand to acrylic plate and fingerprinted acrylic plate with vertical pressure of 250g / ㎠ to attach similar fingerprint.

&Lt;

The texture of the coated film with the similar fingerprint is observed and evaluated by eyes. ?: No fingerprints were seen,?: No fingerprints were seen, but they were seen at specific angles, X: Same as untreated acrylic plates

Surface reflectance

The reflectance of the mirror surface was measured with a spectrophotometer at an angle of incidence of 5 ° and an angle of reflection of 5 ° at 380-780 nm to measure an average reflectance of 450 nm and 60 nm.

Affinity , Hydrophilicity evaluation

In order to evaluate the hydrophilicity and lipophilicity of the obtained coating film, oleic acid was dropped on the substrate surface and the contact angle with the surface of the coating film was measured at room temperature using a contact angle measuring instrument.

Oleic acid contact angle Evaluation of culture Pencil hardness reflectivity Example 1 8 ○ > 9H 0.4

50 g of the functional fine particle solution prepared in Example 1, 100 g of dipentaerythritol hexaacrylate, 5 g of 1-hydroxydicyclohexyl phenyl ketone and 20 g of 2-perfluorohexylethyl methacrylate were mixed to prepare a coating solution.

The solution was coated on a PET film with a bar coater to a thickness of 100 m, dried at 80 DEG C for 1 minute to remove the solvent, and then dried under a mercury lamp (120 W / cm) at an energy of 300 mJ / cm2 to cure the coating. The results for the functionality are as follows (Table 2)

Oleic acid contact angle Evaluation of culture Pencil hardness reflectivity Example 2 5 ○ > 2H 0.5

Functional coating materials such as scratch resistant, fingerprints, and anti-reflective coatings manufactured in this way can be used for mobile phones and tablet PCs as well as electronic products such as TVs, game machines, PMPs, MP3 players, LCD TVs It can also be applied to windows.

The anti-fingerprint and antireflection coating agent according to the present invention is applied to automobile glass coating products, architectural glass products, solar cells and the like other than the surface treatment technology of touch screen for displays. In the current situation where self-cleaning function and light reflection control technology are important for automobile and architectural glass products, and solar cell power generation is limited due to system efficiency due to contamination and reflection on module surface, Is expected to be able to provide a suitable solution for such technical solution needs, and thus is highly industrially applicable.

Claims

MTT (methyl trimethoxy silane) or MAPTMS (methacryloyl aminopropyltri methoxy silane) was added to the mixed solution to prepare a mixed solution by mixing acetone, distilled water and TEA (triethylamine), and the mixture was reacted for 20 to 30 hours to prepare a functional nanoparticle solution (S10), < / RTI >
The functional particle solution prepared in step S10, MTMS, Trifluoropropyltrimethoxysilane (TFPTMS), nitric acid, IPA and distilled water are added and reacted for 20 to 30 hours to prepare a solution of a fingerprint / (S20). &Lt; RTI ID = 0.0 > 11. < / RTI >

The method according to claim 1,
The functional nanoparticle solution is prepared by mixing 80 to 97 wt% of acetone, 2 to 15 wt% of distilled water, and 0.1 to 5 wt% of TEA (triethylamine) to prepare a mixed solution of 100 wt%
And 5 to 30 wt% of MTMS (methyl trimethoxy silane) and 1 to 7 wt% of methacryloyl aminopropyltri methoxy silane (MAPTMS) are added to 69 to 90 wt% of the mixed solution, and the mixture is reacted for 20 to 30 hours. / Method for manufacturing a reflective film.

The method according to claim 1,
The inner fingerprint / anti-reflection coating solution contains 2 to 15 wt% of the functional nanoparticle solution, 55 to 75 wt% of the MTMS, 8 to 20 wt% of the trifluorosilyltrimethoxysilane (TFPTMS), 0.1 to 5 wt% of the nitric acid, And 0.1 to 6 wt% of distilled water for 20 to 30 hours to prepare an inner fingerprint / inner reflection film coating.