KR102204059B1 - Anti-reflective coating composition and anti-reflective coating film using the same - Google Patents

Abstract

The present invention relates to an antireflection coating composition and a coating film using the same. The present invention provides an antireflection coating composition having excellent visible light transmittance, reflectance and hardness, and an antireflection coating film using the same.

Description

Anti-reflective coating composition and anti-reflective coating film using the same}

The present invention relates to an antireflection coating composition and an antireflection coating film using the same.

The display collectively refers to an image display device that implements a variety of information on a screen so that humans can see it. The display industry is an industry that includes all activities necessary for the production of displays and related parts, materials, and equipment.

Flat panel displays are a device industry that requires large-scale investment, and is a high-risk industry that may lose competitiveness if market forecasts fail. It forms a typical supply and demand structure in which parts and materials are supplied, and standardization and standardization issues of front set makers have a huge impact on the display industry.

In the past, coating technology was regarded as a subsidiary technology in the development of finished products such as TVs, monitors, and mobile devices, but recently, it has become a core technology that determines the characteristics of final products. In particular, comprehensive research in the field of development such as the development of coating solutions and process development and selection of raw and subsidiary materials such as base films is important.

Functional films such as optical films are films that have functions such as antistatic, antireflection, contamination, super water repellency, and scratch resistance by secondary processing such as coating or laminate on the base film. It is widely used in batteries and the like. As the type of optical functional film used in displays, as display devices such as LCD and OLED become more advanced and larger, an antireflection film that prevents degradation of image quality due to light reflection, and an antistatic film that prevents the adhesion of foreign substances due to static electricity. Films and super water-repellent films that prevent surface contamination of displays.

As the demand for mobile devices that use touch functions such as smartphones, tablet PCs, and notebooks for optical display films increases, the demand for multifunctional films such as anti-reflective, anti-static, anti-pollution, and scratch-resistance is increasing.

The multifunctional optical film is expanding into home appliances such as TVs, monitors, electronic boards, advertisement displays, refrigerators, etc. as well as mobile devices, which are small and medium-sized home appliances, and the market is increasing, and the solar light is converted by the characteristics of antireflection and pollution resistance. By increasing the efficiency, it can be applied to solar module protection windows.

In general, since the antireflection film is attached to the outermost part of the display, it is necessary to impart antistatic, stain and scratch resistance to the antireflective film through an additional process. Conventional multi-functional anti-reflective film additionally proceeds with a multi-coating or lamination process in which multiple coatings are performed in order to impart anti-fouling and anti-static functions to the layer exhibiting anti-reflection properties, but the present invention is a single process. By providing multi-functions such as anti-reflection, anti-pollution, anti-static, and anti-scratch, and simplifying the process, not only reduces process energy by using minimized energy, but also realizes clear image quality in low contrast, energy efficiency of the display device. Can increase

The present inventors have made intensive research efforts to develop an antireflection coating composition having excellent physical properties such as low refractive index and high visible light transmittance, durability, and stain resistance. As a result, the present invention was completed by finding out that a coating composition prepared using a silica airgel and a perfluoro polymer has an excellent antireflection effect.

Accordingly, it is an object of the present invention to provide an anti-reflective coating composition.

Another object of the present invention is to provide an antireflection coating film using an antireflection coating composition.

According to an aspect of the present invention, the present invention is a silica airgel; And an antireflective coating composition comprising a perfluoro polymer.

The present inventors have made intensive research efforts to develop an antireflection coating composition having excellent physical properties such as low refractive index and high visible light transmittance, durability, and stain resistance. As a result, it was found that a coating composition prepared using a silica airgel and a perfluoro polymer has an excellent antireflection effect.

The silica airgel may be prepared from at least one selected from the group consisting of methyltrimethoxysilane and methyltriethoxysilane. Silica airgel can be prepared in an alcohol solvent by hydrolysis and condensation reaction of polymethyltrialkoxysilane (CH ₂ )n (eg, n=1 to 8). Specifically, the silica aerogel is a gel by mixing methyltrimethoxysilane or methyltriethoxysilane with distilled water, an acid catalyst, and methanol to form a gel, and a solution of the gel and colloidal silica, distilled water and ethanol is mixed and stirred. It can then be obtained by homogenization.

The perfluoro polymer is (a) perfluoro diol; Fluorine-based solvents; Organic solvent; Forming a reaction mixture comprising a monoisocyanate acrylate monomer, a diisocyanate monomer, or a combination thereof; And (b) adding and heating a catalyst.

Steps (a) and (b) of the perfluoropolymer production process may be repeated within the range of 1 to 5 times. For example, when the above process is carried out only once, a perfluoropolymer is formed by the primary polymerization reaction, and when the process is carried out twice, the perfluoropolymer is formed by the primary and secondary polymerization reactions. Is formed.

The reaction mixture of step (a) is formed by stirring at a stirring speed of 100 to 500 rpm, or 200 to 300 rpm, and the stirring temperature is room temperature or room temperature.

The heating of step (b) starts at room temperature and starts at 50 to 150°C, 50 to 120°C, 50 to 100°C, 70 to 150°C, 70 to 120°C, 70 to 100°C, 80 to 150°C, 80 to 120 It consists of a temperature of 80 to 100 ℃ ℃.

In the polymerization reaction of the perfluoro polymer, 5 to 40 parts by weight of perfluoro diol; 30 to 60 parts by weight of a fluorine-based solvent; 5 to 35 parts by weight of monoisocyanate acrylate monomer and/or 5 to 35 parts by weight of diisocyanate monomer; 0.005 to 0.1 parts by weight of a catalyst; And 5 to 15 parts by weight of an organic solvent.

In the polymerization reaction of the perfluoro polymer, 10 to 40 parts by weight of perfluoro diol based on 25 parts by weight of monoisocyanate acrylate monomer; 35 to 55 parts by weight of a fluorine-based solvent; 5 to 30 parts by weight of diisocyanate monomer; 0.005 to 0.1 parts by weight of a catalyst; And 5 to 15 parts by weight of an organic solvent.

In one embodiment of the present invention, in the polymerization reaction of the perfluoro polymer, 10 to 30 parts by weight of perfluoro diol based on 25 parts by weight of monoisocyanate acrylate monomer; 45 parts by weight of a fluorine-based solvent; 5 to 25 parts by weight of diisocyanate monomer; 0.01 to 0.05 parts by weight of a catalyst; And 10 parts by weight of an organic solvent.

In a specific embodiment of the present invention, the polymerization reaction of the perfluoro polymer includes 20 parts by weight of perfluoro diol based on 25 parts by weight of monoisocyanate acrylate monomer; 45 parts by weight of a fluorine-based solvent; 12 parts by weight of diisocyanate monomer; 0.02 parts by weight of catalyst; And 10 parts by weight of an organic solvent.

The organic solvent may be one containing 5:3:1:1 or 6:2:2:1 parts by weight of methyl ethyl ketone, methyl isobutyl ketone, acetone, and ethyl acetate.

The perfluoro diol may be selected from compounds represented by Formula 1:

[Formula 1]

In Formula 1, R is -CH ₂ (CF ₂ )nCH ₂ -, -CH ₂ CF ₂ (OCF ₂ CF ₂ )mOCF ₂ CH ₂ -, -CH ₂ CF ₂ O(CF ₂ CF ₂ O)nCF ₂ CH ₂ -, -CH ₂ CF ₂ O(CF ₂ O)mCF ₂ CH ₂ -, or -CH ₂ CF ₂ O(CF ₂ CFO)n(CF ₂ O)mCF ₂ CH ₂ -, wherein n is 1 to An integer of 8, and m is each independently selected from an integer of 1 to 5.

In one embodiment of the present invention, in Formula 1, R is -CH ₂ CF ₂ O(CF ₂ CFO)n(CF ₂ O)mCF ₂ CH ₂ -, n is 8, and m is 5.

In one embodiment of the present invention, the perfluoro diol is perfluoropolyether-diol (PFPE-diol).

The fluorine-based solvent is one selected from the group consisting of trifluorononanol, trifluorodecanol, tetrafluorononanol, tetrafluorodecanol, methoxy-nonafluorobutane, and ethoxy-nonafluorobutane. It may be more than that.

In one embodiment of the present invention, the fluorine-based solvent is ethoxy-nonafluorobutane.

The isocyanate acrylate monomer may be selected from compounds represented by the following formula (2):

[Formula 2]

In Formula 2, R ₁ is -CH ₂ (CF ₂ )nCH ₂ -, -CH ₂ CF ₂ (OCF ₂ CF ₂ )mOCF ₂ CH ₂ -, -CH ₂ CF ₂ O(CF ₂ CF ₂ O)nCF ₂ CH ₂ -, -CH ₂ CF ₂ O(CF ₂ O)mCF ₂ CH ₂ -, or -CH ₂ CF ₂ O(CF ₂ CFO)n(CF ₂ O)mCF ₂ CH ₂ -, wherein n is an integer of 1 to 8, the m Each is independently selected from an integer range of 1 to 5, and X ₁ is each independently selected from substituents represented by Formulas 3 to 6:

[Formula 3]

,

,

[Formula 4]

,

,

[Formula 5]

, 및

, And

[Formula 6]

.

.

In one embodiment of the present invention, the isocyanate acrylate monomer is 2-isocyanate ethyl methacrylate or isocyanate ethyl acrylate.

The diisocyanate monomer may be selected from compounds represented by the following formula (7):

[Formula 7]

In Chemical Formula 7, R ₂ is -CH ₂ (CF ₂ )nCH ₂ -, -CH ₂ CF ₂ (OCF ₂ CF ₂ )mOCF ₂ CH ₂ -, -CH ₂ CF ₂ O(CF ₂ CF ₂ O)nCF ₂ CH ₂ -, -CH ₂ CF ₂ O(CF ₂ O)mCF ₂ CH ₂ -, or -CH ₂ CF ₂ O(CF ₂ CFO)n(CF ₂ O)mCF ₂ CH ₂ -, wherein n is 1 Integer of to 8, m is each independently selected from the integer range of 1 to 5, X ₁ is each independently selected from the substituents represented by the formulas 3 to 6, Y ₁ is each independently of the following formulas 8 to It is selected from the substituents represented by 23:

[Formula 8]

,

,

[Formula 9]

,

,

[Formula 10]

,

,

[Formula 11]

,

,

[Formula 12]

,

,

[Formula 13]

,

,

[Formula 14]

,

,

[Formula 15]

,

,

[Formula 16]

,

,

[Formula 17]

,

,

[Formula 18]

,

,

[Formula 19]

,

,

[Formula 20]

,

,

[Formula 21]

,

,

[Formula 22]

, 및

, And

[Formula 23]

.

.

In one embodiment of the present invention, the diisocyanate monomer is isophorone diisocyanate.

The organic solvent may be used without limitation as long as it is suitable for dissolving the solid components, and propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), butyl cellosolve (BC), methyl cello Solbu (MC), ethylene glycol (EG), propylene glycol (PG), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), propylene glycol diacetate (PGDA), propylene glycol normal propyl ether (PnP), tetrahydrofuran, toluene, xylene, butyl acetate, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, isopropanol, butanol, butoxyethanol, pentanol, octane It may be selected from the group consisting of ol, hexane, heptane, ether, ketone, and combinations thereof, and may be, for example, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, or a mixture thereof.

The catalyst is not particularly limited as long as it is a catalyst commonly used in the art, and for example, any one or two or more selected from an amine-based catalyst, an organic titanium compound-based, and an organic tin compound-based catalyst may be used, for example , Preferably, dibutyl tin dilaurate or di-n-butylbis (dodecylthio) tin (di-n-butylbis (dodecylthio) tin) may be used as an organotin compound-based catalyst. .

In addition, the anti-reflection coating composition of the present invention may further include additives as needed, and the additives may be used without limitation as long as they are commonly used in the field. More specifically, for example, additives for surface control, antistatic agents, photostimulants, antioxidants, UV absorbers, light stabilizers, thermal polymerization inhibitors, leveling agents, surfactants, lubricants, etc. may further be included, and are limited thereto. It does not become.

According to another aspect of the present invention, the present invention relates to an antireflection coating film comprising an optical film and a coating layer formed by curing after applying the antireflection coating composition to one or both sides of the optical film.

The optical film is triacetyl cellulose, polynorbornene, polyimide, polycarbonate, polyester, polystyrene, polyolefin, polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethacrylate and poly It may be made of one or more selected from the group consisting of ether ketone, polyvinyl alcohol and polyvinyl chloride.

The antireflection coating film may be prepared by mixing a photocuring initiator with the antireflection coating composition and applying it to one or both surfaces of the optical film.

The photocuring initiator is 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyl trichloro acetophenone, ρ-t-butyl Dichloro acetophenone, benzophenone, 4-chloro acetophenone, 4,4' dimethyl amino benzophenone, 4,4'-dichloro benzophenone, 3,3'-dimethyl-2-methoxy benzophenone, 2,2'- Dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholine propanone-1, 2-benzyl-2-dimethyl amino-1-(4-morphopoly Acetophenone compounds such as nophenyl)-butan-1-one and anthraquinone; Benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethyl amino)benzophenone, 4,4'-bis(diethyl amino) Benzophenone compounds such as benzophenone; Thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chloro thioxanthone Thioxanthone compounds such as santon; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethylketal, and the like; 2,4,6,-trichloro s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-S-triazine, 2-(3',4'-dimethoxy styryl)-4, 6-bis(trichloromethyl)-S-triazine, 2-(4'-methoxy naphthyl)-4,6-bis(trichloromethyl)-S-triazine, 2-(p-methoxy phenyl )-4,6-bis(trichloromethyl)-S-triazine, 2-(p-triazine)-4,6-bis(trichloromethyl)-S-triazine, 2-phenyl 4,6-bis (Trichloromethyl)-S-triazine, bis(trichloromethyl)-6-styryl s-triazine, 2-(naphtho 1-yl)-4,6-bis(trichloromethyl)-S- Triazine, 2-(4-methoxy naphtho 1-yl)-4,6-bis(trichloromethyl)-S-triazine, 2-4-trichloromethyl(piperonyl)-6-triazine Triazine compounds such as 2-4-trichloromethyl (4'-methoxy styryl)-6-triazine; Ketone compounds such as diphenyl ketone benzyl dimethyl ketal, 4-hydroxy cyclophenyl ketone, and 1-hydroxy cyclohexyl phenyl ketone; It may be one or more selected from the group consisting of fluorene, triphenyl amine, carbazole, and diphenyl (2,4,6-trimethylbenzoyl) phosphine, and for example, ketone-based and phenone-based compounds may be used together. have.

The present invention relates to an antireflection coating composition and a coating film using the same. The present invention provides an antireflection coating composition having excellent visible light transmittance, reflectance and hardness, and an antireflection coating film using the same.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for describing the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples according to the gist of the present invention. .

Throughout the present specification, "%" used to indicate the concentration of a specific substance is (weight/weight)% for solids/solids, (weight/volume)% for solids/liquids, and Liquid/liquid is (vol/vol) %.

Example

Preparation Example 1-2: Synthesis of silica airgel

Manufacturing Example 1

Methyltrimethoxysilane, distilled water, acid catalyst, and methyl alcohol were mixed in a weight ratio of 140:55:4:36, stirred for 30 minutes, and allowed to stand at room temperature for 24 hours to prepare a gel. Thereafter, to prevent gelation of the gel, a solution was prepared by mixing colloidal silica (Ludox), distilled water, and ethyl alcohol at a weight ratio of 4:16:56, and then at a weight ratio of 1:22 (gel:solution) for 48 hours. Stirring to prepare a stable silica airgel. 10 g of methyl alcohol was mixed thereto, homogenized for 5 minutes, filtered under reduced pressure, and dried overnight at room temperature.

Manufacturing Example 2

Methyl triethoxysilane, distilled water, acid catalyst, and methyl alcohol were mixed in a weight ratio of 140:55:4:36, stirred for 30 minutes, and allowed to stand at room temperature for 24 hours to prepare a gel. Thereafter, to prevent gelation of the gel, a solution was prepared by mixing colloidal silica (Ludox), distilled water, and ethyl alcohol at a weight ratio of 4:16:56, and then at a weight ratio of 1:22 (gel:solution) for 48 hours. Stirring to prepare a stable silica airgel. 10 g of methyl alcohol was mixed thereto, homogenized for 5 minutes, filtered under reduced pressure, and dried overnight at room temperature.

Preparation Example 3-11: Synthesis of perfluoropolymer

Manufacturing Example 3

Perfluorodiol 10 parts by weight of a fluorine-based solvent (ethoxy-nonafluorobutane (C ₄ F ₉ OC ₂ H ₅ )) 45 parts by weight and methyl ethyl ketone, methyl isobutyl ketone, acetone and ethyl acetate are 5:3:1: Add 1 or 6: 2: 2: 1 parts by weight, add 25 parts by weight of 2-isocyanate ethyl methacrylate, add 0.01 parts by weight of dibutyl tin dilaurate as a catalyst in a halogen gas atmosphere, and at room temperature for 20-50 minutes Stirred. Subsequently, the temperature was slowly raised to a maximum of 100° C., 0.01 parts by weight of a catalyst was added, and the reaction time was checked, and polymerization was carried out until the urea reaction was completed.

The polymerization was carried out while stirring at 200-300 rpm in a glass reactor.

Manufacturing Example 4

Perfluorodiol 10 parts by weight of a fluorine-based solvent (ethoxy-nonafluorobutane (C ₄ F ₉ OC ₂ H ₅ )) 45 parts by weight and methyl ethyl ketone, methyl isobutyl ketone, acetone and ethyl acetate are 5:3:1: 1 or 6:2:2: 1 part by weight was added, 6 parts by weight of diisocyanate monomer was added, and 0.01 parts by weight of dibutyl tin dilaurate as a catalyst was added in a halogen gas atmosphere, followed by stirring at room temperature for 20-50 minutes. Subsequently, the temperature was slowly raised to a maximum of 100°C, and the reaction time was checked, and polymerization was carried out until the urea reaction was completed.

After the first polymerization, 25 parts by weight of 2-isocyanate ethyl methacrylate was added, and 0.01 parts by weight of a catalyst was added in a halogen gas atmosphere, followed by stirring at room temperature for 20-50 minutes. Subsequently, the temperature was slowly raised to a maximum of 100°C, and the reaction time was checked, and polymerization was carried out until the urea reaction was completed.

The polymerization was carried out while stirring at 200-300 rpm in a glass reactor.

Manufacturing Example 5

Perfluorodiol 20 parts by weight of a fluorine-based solvent (ethoxy-nonafluorobutane (C ₄ F ₉ OC ₂ H ₅ )) 45 parts by weight and methyl ethyl ketone, methyl isobutyl ketone, acetone, and ethyl acetate are 5:3:1: 1 or 6:2:2: 1 part by weight was added, 12 parts by weight of diisocyanate monomer was added, 0.02 part by weight of dibutyl tin dilaurate as a catalyst was added in a halogen gas atmosphere, and the mixture was stirred at room temperature for 20-50 minutes. Subsequently, the temperature was slowly raised to a maximum of 100°C, and the reaction time was checked, and polymerization was carried out until the urea reaction was completed.

After the first polymerization, 25 parts by weight of 2-isocyanate ethyl methacrylate was added, and 0.02 parts by weight of a catalyst was added in a halogen gas atmosphere, followed by stirring at room temperature for 20-50 minutes. Subsequently, the temperature was slowly raised to a maximum of 100° C. to check the reaction time, and polymerization was carried out until the urea reaction was completed.

The polymerization was carried out while stirring at 200-300 rpm in a glass reactor.

Manufacturing Example 6

Perfluorodiol 30 parts by weight of a fluorine-based solvent (ethoxy-nonafluorobutane (C ₄ F ₉ OC ₂ H ₅ )) 45 parts by weight and methyl ethyl ketone, methyl isobutyl ketone, acetone, and ethyl acetate are 5:3:1: 1 or 6:2:2: 1 part by weight was added, 18 parts by weight of diisocyanate monomer was added, 0.03 parts by weight of dibutyl tin dilaurate as a catalyst was added in a halogen gas atmosphere, and the mixture was stirred at room temperature for 20-50 minutes. Subsequently, the temperature was slowly raised to a maximum of 100° C. to check the reaction time, and polymerization was carried out until the urea reaction was completed.

After the first polymerization, 25 parts by weight of 2-isocyanate ethyl methacrylate was added, and 0.03 parts by weight of a catalyst was added in a halogen gas atmosphere, followed by stirring at room temperature for 20-50 minutes. Subsequently, the temperature was slowly raised to a maximum of 100° C. to check the reaction time, and polymerization was carried out until the urea reaction was completed.

The polymerization was carried out while stirring at 200-300 rpm in a glass reactor.

Manufacturing Example 7

Perfluorodiol 40 parts by weight of a fluorine-based solvent (ethoxy-nonafluorobutane (C ₄ F ₉ OC ₂ H ₅ )) 45 parts by weight and methyl ethyl ketone, methyl isobutyl ketone, acetone and ethyl acetate are 5:3:1: 1 or 6:2:2:1 parts by weight were added, and 22 parts by weight of diisocyanate monomer was added, and 0.04 parts by weight of dibutyl tin dilaurate as a catalyst was added in a halogen gas atmosphere, followed by stirring at room temperature for 20-50 minutes. Subsequently, the temperature was slowly raised to a maximum of 100°C, and the reaction time was checked, and polymerization was carried out until the urea reaction was completed.

After performing the first polymerization, 25 parts by weight of 2-isocyanate ethyl methacrylate was added, 0.04 parts by weight of a catalyst was added in a halogen gas atmosphere, and the mixture was stirred at room temperature for 20-50 minutes. Subsequently, the temperature was slowly raised to a maximum of 100°C, and the reaction time was checked, and polymerization was carried out until the urea reaction was completed.

The polymerization was carried out while stirring at 200-300 rpm in a glass reactor.

Manufacturing Example 8

In Preparation Example 3, the polymerization was carried out in the same manner as in Preparation Example 3 except that 2-isocyanate ethyl methacrylate was changed to 2-isocyanate ethyl acrylate.

Manufacturing Example 9

In Preparation Example 4, the polymerization was carried out in the same manner as in Preparation Example 4, except that 2-isocyanate ethyl methacrylate was changed to 2-isocyanate ethyl acrylate.

Manufacturing Example 10

In Preparation Example 5, the polymerization was carried out in the same manner as in Preparation Example 5 except that 2-isocyanate ethyl methacrylate was changed to 2-isocyanate ethyl acrylate.

Manufacturing Example 11

In Preparation Example 6, the polymerization was carried out in the same manner as in Preparation Example 6 except that 2-isocyanate ethyl methacrylate was changed to 2-isocyanate ethyl acrylate.

Manufacturing Example 12

Polymerization was carried out in the same manner as in Preparation Example 7, except that 2-isocyanate ethyl methacrylate was changed to 2-isocyanate ethyl acrylate in Preparation Example 7.

As the perfluoro diol, PFPE-Diol (Solvay Solexis, Mn=3800 g/mol) was used. Isophorone diisocyanate (Sigma Aldrich Mn=222.3 g/mol) was used as the diisocyanate.

The polymerization ratio is shown in Table 1.

- Perfluoro diol Fluorine solvent menstruum Diisocyanate monomer Catalyst Monoisocyanate acrylate monomer Kinds input Manufacturing Example 3 10 45 10 - 0.01 2-isocyanate ethyl methacrylate 25 Manufacturing Example 4 10 45 10 6 0.01 25 Manufacturing Example 5 20 45 10 12 0.02 25 Manufacturing Example 6 30 45 10 18 0.03 25 Manufacturing Example 7 40 45 10 22 0.04 25 Manufacturing Example 8 10 45 10 - 0.01 2-isocyanate ethyl acrylate 25 Manufacturing Example 9 10 45 10 6 0.01 25 Manufacturing Example 10 20 45 10 12 0.02 25 Manufacturing Example 11 30 45 10 18 0.03 25 Manufacturing Example 12 40 45 10 22 0.04 25

Example 1-10: Preparation of antireflection coating film

3 parts by weight of the silica airgel prepared in Preparation Example 1 and 97 parts by weight of the perfluoropolymer prepared in Preparation Example 3-12 were mixed to prepare an antireflection coating composition.

Photocuring initiator 1-hydroxycyclohexyl phenyl ketone (1-Hydroxycyclohexyl phenyl ketone, Sigma Aldrich Mn = 204.3 g/mol) and diphenyl (2,4) per 100 parts by weight of a mixture of silica airgel and perfluoropolymer. ,6-trimethylbenzoyl)phosphine oxide (Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, Sigma Aldrich Mn=348.4 g/mol) was mixed in a 2:1 ratio of 1.0 to 2.5 parts by weight of a mixture. After coating on one side of a 125 ㎛-thick optical film (Toray XG7PL2), dry it at 70-80℃ for 3 minutes, and cure it with a high-pressure mercury lamp with an illuminance of 80 W/cm ^{2 and a} light intensity of 400-1000 mJ/cm ² . A coating layer of μm was formed. The blending ratio is shown in Table 2.

Example 11-20: Preparation of antireflection coating film

An antireflection coating composition was prepared by mixing 3 parts by weight of the silica airgel prepared in Preparation Example 2 and 97 parts by weight of the perfluoropolymer prepared in Preparation Example 3-12.

Photocuring initiator 1-hydroxycyclohexyl phenyl ketone (1-Hydroxycyclohexyl phenyl ketone, Sigma Aldrich Mn = 204.3 g/mol) and diphenyl (2,4) per 100 parts by weight of a mixture of silica airgel and perfluoropolymer. ,6-trimethylbenzoyl)phosphine oxide (Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, Sigma Aldrich Mn=348.4 g/mol) was mixed in a 2:1 ratio of 1.0 to 2.5 parts by weight of a mixture. After coating on one side of a 125 ㎛-thick optical film (Toray XG7PL2), dry it at 70-80℃ for 3 minutes, and cure it with a high-pressure mercury lamp with an illuminance of 80 W/cm ^{2 and a} light intensity of 400-1000 mJ/cm ² . A coating layer of μm was formed. The blending ratio is shown in Table 2.

Silica airgel Perfluoro polymer Photoinitiator Drying condition
(℃) Curing conditions
(mJ/cm ² ) Kinds input Kinds input Example 1 Manufacturing Example 1 3 Manufacturing Example 3 97 One 80 550 Example 2 3 Manufacturing Example 4 97 2 80 650 Example 3 3 Manufacturing Example 5 97 2 80 700 Example 4 3 Manufacturing Example 6 97 2.5 80 800 Example 5 3 Manufacturing Example 7 97 2.5 80 850 Example 6 3 Manufacturing Example 8 97 One 80 550 Example 7 3 Manufacturing Example 9 97 2 80 650 Example 8 3 Manufacturing Example 10 97 2 80 700 Example 9 3 Manufacturing Example 11 97 2.5 80 800 Example 10 3 Manufacturing Example 12 97 2.5 80 850 Example 11 Manufacturing Example 2 3 Manufacturing Example 3 97 One 80 550 Example 12 3 Manufacturing Example 4 97 2 80 650 Example 13 3 Manufacturing Example 5 97 2 80 700 Example 14 3 Manufacturing Example 6 97 2.5 80 800 Example 15 3 Manufacturing Example 7 97 2.5 80 850 Example 16 3 Manufacturing Example 8 97 One 80 550 Example 17 3 Manufacturing Example 9 97 2 80 650 Example 18 3 Manufacturing Example 10 97 2 80 700 Example 19 3 Manufacturing Example 11 97 2.5 80 800 Example 20 3 Manufacturing Example 12 97 2.5 80 850

Experimental Example 1: Transmittance (%)

A sample of the film was taken and the transmittance and haze were measured using COH400 manufactured by Nippon Denshoku.

Experimental Example 2: Contact angle

The volume of water was dropped in the middle of a 600 µl/min sample in a size of 3 µl and the contact angle was measured after 3 seconds.

Experimental Example 3: Pencil hardness

Pencils of various hardnesses specified in KSG 2603 were placed at an angle of 45 degrees on the coated test sample, and the degree of damage to the surface was measured by scratching with a load of the specified weight (1,000 g).

Experimental Example 4: Coating thickness

After pressurizing for 5 seconds with a pressure of 20±0.2 kPa with a thickness gauge, cut the first 300 mm part in the manufacturing direction of the product, and then cut off the part 20 mm from the end to both ends, 10% inside each width The thickness was measured to 0.01 mm at 10 locations, which was the sum of the 2 points entered by and the 8 points between the 9th place, and the average value of the measurements was obtained.

Experimental Example 5: refractive index

The refractive index of light at a wavelength of 633 nm was measured using an Eripsometer DVA-36L manufactured by Mizojiri Optical Co., Ltd.

Experimental Example 6: Measurement of reflectance

Using an ultraviolet spectrophotometer V-770 of Jasco Corporation, the reflectance of light at an incidence angle of 5 degrees of light having a wavelength of 380-780 nm in the visible region was measured.

- Coating thickness (μm) Water contact angle Pencil hardness Refractive index reflectivity(%) Transmittance (%) Haze (%) Example 1 5 112.5 2H 1.257 0.26 93.8 0.7 Example 2 5 123.7 2H 1.280 0.54 93.1 0.6 Example 3 5 132.1 3H 1.332 0.89 94.3 0.7 Example 4 5 131.5 3H 1.365 1.78 92.5 1.1 Example 5 5 132.7 3H 1.382 2.54 91.8 1.8 Example 6 5 102.3 2H 1.259 0.53 92.4 0.8 Example 7 5 113.5 2H 1.291 0.88 92.6 0.8 Example 8 5 118.4 3H 1.340 1.71 92.8 0.9 Example 9 5 118.9 3H 1.355 1.98 92.1 1.2 Example 10 5 119.2 3H 1.371 2.43 91.9 2.0 Example 11 5 113.5 2H 1.255 0.57 91.9 0.8 Example 12 5 125.8 2H 1.281 0.77 91.7 0.9 Example 13 5 131.2 3H 1.333 1.34 91.5 1.1 Example 14 5 131.5 3H 1.364 1.58 92.1 1.2 Example 15 5 132.3 3H 1.376 2.11 91.7 1.1 Example 16 5 101.5 2H 1.246 0.48 91.5 0.7 Example 17 5 110 2H 1.274 0.52 91.9 0.7 Example 18 5 111.8 3H 1.302 0.91 92.2 0.9 Example 19 5 111.7 3H 1.332 1.14 92.5 1.1 Example 20 5 113.5 3H 1.345 1.53 92.4 1.5

The higher the water contact angle, the more the surface contamination of the display can be prevented, and the higher the transmittance and the lower the haze, the more light is diffused and clearer. Also, if the pencil hardness is high, it reduces scratches or scratches on the film. In addition, the reflectance is attached to the outer surface of the display to prevent the phenomenon that external light is reflected on the surface of the film, thereby increasing the visibility of the screen, and the lower the reflectivity, the greater the effect.

As shown in Table 4, the results of Example 1-5 were the best, among which the antireflection film prepared in Example 3 exhibited high water contact angle, pencil hardness and transmittance, and low refractive index, reflectance and haze Showed the most excellent physical properties.

Claims (10)

Silica airgel; And as an anti-reflective coating composition comprising a perfluoro polymer,
The silica airgel is prepared from at least one selected from the group consisting of methyltrimethoxysilane and methyltriethoxysilane,
The perfluoro polymer is
(a) perfluoro diol; Fluorine-based solvents; Organic solvent; Forming a reaction mixture comprising a monoisocyanate acrylate monomer, a diisocyanate monomer, or a combination thereof; And
(b) is produced by a polymerization reaction step of adding and heating a catalyst,
The perfluoro diol is selected from compounds represented by the following formula (1), antireflection coating composition:
[Formula 1]

In Formula 1, R is -CH ₂ (CF ₂ )nCH ₂ -, -CH ₂ CF ₂ (OCF ₂ CF ₂ )mOCF ₂ CH ₂ -, -CH ₂ CF ₂ O(CF ₂ CF ₂ O)nCF ₂ CH ₂ -, -CH ₂ CF ₂ O(CF ₂ O)mCF ₂ CH ₂ -, or -CH ₂ CF ₂ O(CF ₂ CF ₂ O)n(CF ₂ O)mCF ₂ CH ₂ -, wherein n is An integer of 1 to 8, wherein m is each independently selected from an integer range of 1 to 5, antireflection coating composition.
delete delete delete The method of claim 1, wherein the fluorine-based solvent is trifluorononanol, trifluorodecanol, tetrafluorononanol, tetrafluorodecanol, methoxy-nonafluorobutane and ethoxy-nonafluorobutane. One or more selected from the group consisting of, antireflection coating composition.
The antireflection coating composition according to claim 1, wherein the organic solvent is methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, or a mixture thereof.
The antireflection coating composition according to claim 1, wherein the monoisocyanate acrylate monomer is a compound represented by the following formula (2):
[Formula 2]

In Formula 2, R ₁ is -CH ₂ (CF ₂ )nCH ₂ -, -CH ₂ CF ₂ (OCF ₂ CF ₂ )mOCF ₂ CH ₂ -, -CH ₂ CF ₂ O(CF ₂ CF ₂ O)nCF ₂ CH ₂ -, -CH ₂ CF ₂ O(CF ₂ O)mCF ₂ CH ₂ -, or -CH ₂ CF ₂ O(CF ₂ CF ₂ O)n(CF ₂ O)mCF ₂ CH ₂ -, wherein n is an integer of 1 to 8, Each m is independently selected from an integer range of 1 to 5, and X ₁ is each independently selected from substituents represented by the following formulas 3 to 6:
[Formula 3]

,

[Formula 4]

,

[Formula 5]

, And

[Formula 6]

.
The anti-reflective coating composition of claim 1, wherein the diisocyanate monomer is selected from compounds represented by the following formula (7):
[Formula 7]

In Chemical Formula 7, R ₂ is -CH ₂ (CF ₂ )nCH ₂ -, -CH ₂ CF ₂ (OCF ₂ CF ₂ )mOCF ₂ CH ₂ -, -CH ₂ CF ₂ O(CF ₂ CF ₂ O)nCF ₂ CH ₂ -, -CH ₂ CF ₂ O(CF ₂ O)mCF ₂ CH ₂ -, or -CH ₂ CF ₂ O(CF ₂ CF ₂ O)n(CF ₂ O)mCF ₂ CH ₂ -, and the n Is an integer of 1 to 8, m is each independently selected from an integer range of 1 to 5, X ₁ is each independently selected from substituents represented by the following formulas 3 to 6, and Y ₁ is each independently the following formula It is selected from substituents represented by 8 to 23:
[Formula 3]

,

[Formula 4]

,

[Formula 5]

,

[Formula 6]

,

[Formula 8]

,

[Formula 9]

,

[Formula 10]

,

[Formula 11]

,

[Formula 12]

,

[Formula 13]

,

[Formula 14]

,

[Formula 15]

,

[Formula 16]

,

[Formula 17]

,

[Formula 18]

,

[Formula 19]

,

[Formula 20]

,

[Formula 21]

,

[Formula 22]

, And

[Formula 23]

.
An antireflection coating film comprising an optical film and a coating layer formed by curing after applying the antireflection coating composition of any one of claims 1 and 5 to 8 on one or both surfaces of the optical film.
The method of claim 9, wherein the optical film is triacetyl cellulose, polynorbornene, polyimide, polycarbonate, polyester, polystyrene, polyolefin, polysulfone, polyethersulfone, polyarylate, polyetherimide, poly Methyl methacrylate and polyether ketone, polyvinyl alcohol and polyvinyl chloride to be made of one or more selected from the group consisting of, anti-reflection coating film.