TW201200562A - Light-curable vinyl-fluoro-siloxane oligomer and antireflection coating composition containing the same - Google Patents

Abstract

An oligomer having an inorganic silicon-oxygen backbone and having vinyl groups and fluoride groups for serving as an oligomer in an light-curable antireflection coating composition. Organic molecules with a fluoro group having a relatively low refraction index may be additionally added to serve as a reactive monomer. The light-cured antireflection film formed by utilizing such composition has excellent physical properties and low reflectance.

Description

201200562 VI. Description of the Invention: [Technical Field] The present invention relates to a compound for producing an anti-reflective coating, and particularly to an oligomer of a photoactive ethylene fluorocarbazone oxide and containing the oligomer The coating composition of the article is used to form an antireflection film. [Prior Art] A Lu anti-reflective film (also referred to as a low reflection film) is often used in a display of an optical element or a display device to reduce light reflectance and enhance display. Conventional antireflective films contain a fluorine-containing compound. Because the refractive index of the fluoride film is lower than that of the substrate, and the phase difference between the reflected light and the light reflected by the underlying hard coating (har (jcoat/HC) can reach 180., the reflected light at the two interfaces can be destroyed. Sexual interference 'is achieved the purpose of reducing light reflection. · Republic of China Patent No. 1251615 discloses a low reflectivity film having a nanostructure, the principle of which is to make a structural change such as engraving on the surface of the film, thereby causing a change in refractive index. However, this method is cumbersome and costly in the process. In addition, it is disclosed in U.S. Patent Application Publication No. US2006/0099407, after modifying the surface of the nanoparticle to a reactive terminal functional group, The rice particles are stacked on each other to form a low-reflectivity film, but the film has a high haze value, and the structure is loose due to a large number of pores in the structure, resulting in insufficient physical properties such as wear resistance. 201200562 A method of coating a fluorinated or a fluorine-based polymer having a specific structure is disclosed in Japanese Patent Laid-Open No. SHO 61 and Special Essence 6. The amount of the Duncan compound often leads to a poor moisturizing effect and a lack of physical properties. Another low-light reflectance film manufacturing method is disclosed in U.S. Patent No. 6,47, 2,012, which requires a high temperature treatment of 420 〇C. Suitable for _ on substrates that are not resistant to high temperatures such as eccentricity. U.S. Patent No. 6,773,121 t discloses financial use (10) fine gel/gel (s〇l ge丨) precursor mono-containing Wei-wei weiss The anti-reflective film is prepared by the kinetic conversion of the gel; the anti-reflective film is obtained; and the fine anti-anti-aliasing is obtained, and the organic compound, such as green-burning carbonic acid, is disclosed in U.S. Patent Application Publication No. 2G07/0172763. The base or the fluorine-containing ethylene material is used for the photocuring reaction, and the anti-reflective film is not as good as the heat. It is known that the anti-reflection or low-fragility material contains fluoride to reduce the refraction. The rate 'but its refractive index is still as high as 14 or 〖5. Therefore, there is still a need for a novel composition for producing an antireflection film having a lower refractive index, but still having appropriate physical properties such as hardness and wear resistance. SUMMARY OF THE INVENTION One object of the present invention is to provide Antireflective coating composition and oligomer of photoactive vinyl fluoride-based cerium oxide contained therein, the antireflection film formed by curing the coating formed by using the antireflective coating composition has good low reflection Rate, and haze value, hardness, and adhesion to the underlayer. The oligomer of the photoactive vinyl fluoride-based ruthenium oxide according to the present invention includes the following compound represented by the chemical formula (I): 201200562, represented by the chemical formula (π) a reaction product of a compound and a compound represented by the formula (III):

RO

Γ OR -Si -0 OR x

OR Si-OR OR (I)

H2C=c

OR Si-〇 R (II) OR 0 - _ 0 -C—一 0-一 —ch2- —Si — Z _ y 〇 (III)

Wherein each R is independently selected from the group consisting of a decyl group, an ethyl group, and a propyl group, and R is selected from the group consisting of hydrogen, a thiol group, and an ethyl group, and X is an integer from 〇 to 17, „ Is an integer from 1 to 1 ,, η is an integer from 1 to 7, Z is 0 or 1, and y is an integer from 〇 to 5. The antireflective coating composition according to the present invention comprises a photoactive vinyl as described above An oligomer of a fluorine-based ruthenium oxide, a photoinitiator, and a diluent solvent. The present invention uses an oligomer of inorganic oxime having a vinyl group and a fluorine group as the anti-reflective coating combination of 201200562. _ oligomer, or can further add a lower refractive index of the organic gas-containing molecule as a reactive monomer. The photocurable antireflective film formed by the ruthenium-like complex has good physical properties and low [Embodiment] The anti-reflective composition according to the present invention comprises an oligomer having a silky ethyl sulfonium ruthenium oxide, a photoinitiator, and a diluent solvent, and may further include photoactive activity. a fluorine-based reaction monomer. The photoactive vinyl fluoride-based ruthenium oxide oligomer is One product was a compound, the compound represented by formula (II), and the chemical structure of Formula column, i.e., represented by the formula (I) (i.e. as represented by the reaction.

OR

OR

RO

Si--〇 _

OR

-Si-OR x

OR (I) wherein each R is independently selected from the group consisting of a thiol group, an ethyl group, and a propyl group. \ is an integer of 〇17, but considering the properties of the antireflection film formed, three or more oligomers formed by the shixi oxygen compound, the physical properties of the obtained antireflection film are better. Therefore, X is preferably an integer of from 3 to 17. 201200562

OR

F3c CF2---CH2--Si-OR mn 〇R (Π) wherein each R is independently selected from the group consisting of a thiol group, an ethyl group, and a propyl group, and 111 is from 1 to 10, preferably An integer from 2 to 7, wherein n is an integer from 1 to 7, preferably from 2 to 5.

H2C=c "0"0 - 0 -C-〇-一-CH2·-Si - · Ζ _ y 〇(ΠΙ) wherein each R is independently selected from the group consisting of a thiol group, an ethyl group, and a propyl group. r, is selected from the group consisting of hydrogen, methyl, and ethyl, 2 is 〇 or 卜 and y is 整数 to the integer 0 of 5. The above three structures can be sol-gel reaction at any ratio. An oligomer of a photoactive vinyl fluoride-based ruthenium oxide according to the present invention can be obtained. Preferably, a compound of the formula (I), a compound of the formula, and a formula (III) The molar ratio of the reaction of the three compounds may be, for example, (2 to 5) (3 to illusion ~). First, the compound represented by the chemical formula (I) and the compound represented by the chemical formula (π) are used as the initiator. In the presence of 'polymerization, forming clusters', the network structure of the galvanic oxygen is a good physical property, and the fluorine-containing compound in the compound represented by the chemical formula (π) becomes a group __' The effect of the refractive index. After that, the compound represented by the chemical ^ 201200562 (III) is added to the cluster formed by the polymerization reaction to continue the reaction. The oligomer of the photoactive vinyl fluoride-based ruthenium oxide according to the present invention can be formed. Thus, the periphery of the oligomer can have a terminal group of a ethyl bond or a propylene bond, and the inside of the polymer is a stone. The network structure of the oxy-oxygen is the main structure. The molecular weight of the oligomer is preferably in the range of 1000 to 5 Å, and when the molecular weight is too large, the refractive index becomes large, and when it is too small, film formation is impossible. The ruthenium bond may serve as a functional group for providing crosslinking in the photoreaction in the subsequent reaction for forming the coating to cure the coating. In the antireflective coating composition, a reaction sheet having a photoactive fluorine group may be further included. A body such as a vinyl monomer having a fluorine-containing alkyl group or a fluorine-containing acrylic monomer having a photocurable reaction can make the formed antireflection film have a lower refractive index and obtain a lower refractive index. Light reflectance. The compound represented by the chemical formula (π) in the above-mentioned oligomer of the photoactive vinyl fluoride-based ruthenium oxide and the further reacting monomer having a photoactive fluorine group in the antireflective coating composition The amount in the matter will affect the The refractive index and the supporting strength of the antireflection film, so the addition ratio varies depending on the properties to be applied to the antireflection film. For example, when the amount thereof is increased, the refractive index of the formed antireflection film can be lowered. Obtaining a lower light reflectivity, but relatively reducing the wear resistance of the material, or reducing the overall support strength of the material. Therefore, the content of the two in the anti-reflective coating composition is a balanced design The photoinitiator is a photocuring 201200562 reaction of an oligomer of a photoactive vinyl fluoride ruthenium oxide or an oligomer of a photoactive vinyl fluoride ruthenium oxide. The photoactive fluorine-based reaction monomer is required to carry out a photocuring reaction together. A suitable photoinitiator is a radical type which is added in an amount of from about 1% by weight to about 1% by weight of the reactive monomer'. CIBA is often used in a range of products for photocurable coatings, such as Chivacure 173 and Chivacure 115, or as shown in Figure 1. Suitable diluent solvents can be, for example, isopropyl (is〇pr〇pyl acetone, IPA), methyl isobutyl ketone 'MIBK, ethyi acetate ( EAC), butyl acetate , BAC), t〇luene, cyclohexanone, methanol or pr〇pylene glycol monoethyl ether acetate (PGMA) or both The solvent is mixed in any ratio, but is not limited thereto, as long as the solvent does not cause phase separation, compatibility, and preferably has low volatility, and the composition component can be dispersed, and the formed resistance The wettability of the reflective film can be used if it is acceptable. The amount of the solvent to be diluted in the antireflective coating composition may be, for example, 9 Å by weight and 99% by weight. By mixing the oligomer of the above photoactive vinyl fluoride ruthenium oxide, the reactive monomer having a photoactive fluorine group (if included), a photoinitiator, and a diluent solvent, the present invention can be obtained. Anti-reflective coating composition. The anti-reflective coating composition of the present invention is suitable for use in applications where an anti-reflective layer is required, such as an optical element-indicator (10) screen. Usually, a hard bonding layer is formed on a substrate, for example, a transparent substrate, and the coating liquid of the antireflective coating composition is applied to the hard 201200562 ore layer to form a film by photocuring. The thickness of the anti-reflective coating composition can be varied depending on the wavelength of the light to be reflected, so that a specific film thickness is applied to the transparent plastic substrate to reduce the reflection of light. The following examples illustrate the fabrication of oligomers and antireflective coating compositions of photoactive vinyl fluoride-based cerium oxides according to the present invention, but the present invention can be applied to a wide variety of different fields. Thus, the examples are only The specific embodiments used to illustrate and make the invention are not intended to limit the invention. EXAMPLES Example 1 Synthesis of oligomers of vinyl fluoride ruthenium oxide Please refer to Fig. 2 '25 g (g) Ethyl-Silicate 48 and 25 g (10) manufactured by Japan COLCOAT Co., Ltd. Tridragon-1,1,2,2-tetrahydrooctyl)tridecafluoro-1,1,2,2-tetrahydrooctyltrimethoxysilane is added to 100 grams of isopropyl solvent as a reaction solvent. Alcohol (isopropano IPA) and 35 g of 0.1 N aqueous HCl solution in a reaction flask 'stirred at room temperature for 30 minutes with a stirrer until completely homogeneous' and then homogenous clear solution at 90 ° C reaction temperature After continuous reaction for 5 hours, the temperature was lowered to room temperature, and 2 g of pre-hydrolyzed vinyltrimethoxysilane was added, and the mixture was continuously stirred at room temperature for 24 hours, and finally a microfilter having a pore size of 〇.45 μm was finally used. The solution obtained by filtration is a solution containing an oligomer of a photoactive vinyl fluoride-based cerium oxide, which is collected and then refrigerated for use. Example 2 Manufacture of Antireflective Coating Composition 201200562 30 g of an oligomer solution of a photoactive vinyl fluoride ruthenium oxide having a concentration of 10% by weight, 10 g of LightEster M-3F (a fluorine-based acrylic monomer) , product of Kyoeisha Chemical Co. Ltd. (40 g of isopropyl alcohol, and 20 g of butanol were stirred in a container, and 3 g of Chivacure 173 and 1 g of Chivacure 115 were added. As an initiator, an antireflective coating composition according to the present invention is formed. Example 3 Production of Antireflective Coating Composition 30 g of a photoactive vinyl fluorobase oxide oligomer solution having a concentration of 1 〇 wt% 10 g of Linc-102A (a fluorine-based acrylic monomer, product of Kyoeisha Chemical Co., Ltd.), 40 g of isopropyl alcohol, and 20 g of butanol were placed in a container and stirred, and 3 g of Chivacure 173 and 1 gram of Chivacure 115 were used as initiators to form an antireflective coating composition according to the present invention. Example 4 Production of Antireflective Coating Composition 30 g of a photoactive vinyl fluoride group having a concentration of 1% by weight Oxide oligomer solution, 40 g of isopropanol And 20 g of butanol were placed in a container, and 3 g of Chivacure 173 and 1 g of Chivacure 115 were added as a starting agent to form an antireflective coating composition according to the present invention. Comparative Example 10 g of a hexafunctional group was used. Polyurethane acrylate UA-306A (product of Sakamoto Kyoritsu Chemical Co., Ltd.), 10 g of Light Ester M-3F, and 60 g of isopropyl alcohol, 201200562 and adding 3 grams of Chivacure 173 and 1 gram of Chivacure 115 As a starter, a composition is formed for comparison. Example 5 The formation of the antireflection film is first performed on the coated substrate. That is, a layer of thickness is applied to the TAC (triacetate) substrate. Hard coating of about 5 to 6/zm, in order to improve the wetting between the anti-reflective coating and the hard ore layer material, TAC/HC (triacetate/hard) is required before coating the anti-reflective coating. The coating layer is immersed in an aqueous solution of potassium hydroxide (KOH) at a concentration of about 8% at 55 ° C for 1 to 2 minutes, then rinsed several times with pure water, and finally dried in a circulating oven for use. Then, Example 2 is respectively The antireflective coating composition according to the present invention and the composition of the comparative example are in the chamber After mixing for 1 minute, apply a 4 wire bar to the pre-treated substrate. Place the 80 C box for 2 minutes, then use UV light with an energy of about 6 〇〇mj/cm2. After curing for about 10 seconds, an antireflection film can be obtained. Test Example Lu 1. Measurement of reflectance: The back surface of the antireflection film obtained above (Dingba (: face) is sprayed with black paint, and the model number is U-4100 (Japan) Hitachi's uv spectrometer measures incident light with a wavelength between 380 nm and 780 nm at 5. The spectral reflectance of the angle. 2. Light transmittance and haze value: 12 201200562 Each antireflection film was directly tested by Haze meter NDH2000 (manufactured by Nippon Denshoku Co., Ltd.). 3. Adhesion measurement: The adhesion of each antireflection film was measured in accordance with the standard test method of JIS K-6801. 4. Pencil Hardness Test The hardness of each anti-reflective film was tested with a hardness tester Scratch Hardness Tester Model 291 (Germany • ERICHSEN). The load used in the measurement was 500 g, and the pencil hardness was 3 Torr. 5. Measurement results Table 1

Sample code 3 Tiger reflectivity penetration rate 1 degree value Adhesive hardness (R), % (Τ), % (haze) (adhesion) (hardness) Example 2 1.51 94.57 0.31 100/100 3H Example 3 1.62 94.03 0.28 100/ 100 3H Example 4 1.75 93.15 0.21 100/100 3H Comparative Example 3.09 92.11 0.29 100/100 3H From the measurement results shown in Table 1, it is understood that Examples 2 and 3 are composed of the photoactive vinyl fluoride-based ruthenium oxide according to the present invention. The antireflective coating prepared by the antireflective coating composition of the oligomer and the photoactive fluorine-based reactive monomer has a lower reflectance (R) of 13 201200562 and a higher transmittance ( Τ), the properties of haze value, adhesion, and hardness can meet the requirements. Embodiment 4 is an antireflection film prepared from an antireflective coating composition containing an oligomer of a photoactive vinyl fluoride ruthenium oxide according to the present invention (a reaction monomer having no photoactive fluorine group) The reflectivity and transmittance are not bad, and each property can meet the requirements. The composition of the comparative example does not contain the oligomer of the photoactive vinyl fluoroantimony oxide according to the present invention, and does not contain the reactive monomer having a photoactive fluorine group, and the antireflection film prepared therefrom , the nature is poor, that is, the reflectivity is higher and the penetration rate is lower. The above are only the preferred embodiments of the present invention, and all changes and modifications made to the scope of the present invention should fall within the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows an example of a photoinitiator suitable for use in the antireflective coating composition according to the present invention. Fig. 2 is a schematic flow chart showing an example of the preparation of an oligomer of a photoactive vinyl fluoride-based ruthenium oxide according to the present invention. [Main component symbol description] No component symbol.

Claims (1)

201200562 VII. Patent application scope: 1. An oligomer of photoactive vinyl fluoride-based ruthenium oxide, comprising a compound represented by the following chemical formula (I), a compound represented by the chemical formula (II), and a compound represented by the chemical formula (III) A reaction product: RO x OR Si - 〇OR OR Si - OR OR OR (I) F3C-kCF2 OR OR (Π) R' H2C=c. 0 - - 〇-C-〇-一-ch2- —Si Z «· y 〇•Si——OR (ΙΠ) wherein each R is independently selected from the group consisting of a decyl group, an ethyl group, and a propyl group, and R is selected from the group consisting of hydrogen, fluorenyl, and ethyl. The group consisting of x is an integer from 〇 to 17, m is an integer from i to 10, 'η is an integer from 1 to 7, and 2 is an integer of 〇 or 卜 and up to 5. 2. The oligomer of the photoactive vinyl fluoride-based ruthenium oxide according to claim 1, wherein the compound represented by the formula (I) and the compound represented by the formula (II) are polymerized and reconciled with the formula 15 201200562 ( The compound represented by III) is polymerized to form the reaction product. 3. An anti-reflective coating composition' comprising an oligomer of a photoactive ethylene, a gas-based cerium oxide thereof as claimed in claim 1, a photoinitiator, and a diluent solvent. Further comprising at least one reactive monomer having light, such as the antireflective coating composition of claim 3, active fluorine groups. 5. The antireflective coating composition according to claim 4, wherein the photoactive dunk-based reactive monomer comprises a fluorine-based monomer having a viscotable photo-curable reaction or a fluorine-containing group. Cree series monomer. Eight, round: 16