TWI580739B - Anti-reflection coating composition and anti-reflection film - Google Patents

Description

Anti-reflective coating composition and anti-reflection film

This invention relates to a coating composition, and more particularly to an antireflective coating composition and an antireflective film made therefrom.

The lenses of telescopes, cameras, and cameras that are commonly used today are optical components. In general, when light is incident on different media, penetration, absorption, reflection, etc. occur, and excessive light will interfere with each other after reflection. For example, the camera lens may have a dull color due to excessive reflected light, which may result in the inability to capture the correct color of the image through the lens.

In order to solve the aforementioned problems, in the prior art, an anti-reflection film is formed by forming a film having a refractive index lower than that of the carrier plate on a carrier (for example, glass, plastic, or the like) to reduce the reflectance. The film having a lower refractive index may include a single layer film structure formed by vacuum evaporation of magnesium fluoride (MgF ₂ ) having a lower refractive index, or by pressing various refractive index films. The resulting multilayer film structure in which a multilayer film structure is formed by a vacuum evaporation method belonging to a vacuum technique will require a high manufacturing cost.

In addition, a method of forming a low refractive index film by using a wet coating such as spin coating or dipping is disclosed in Japanese Laid-Open Patent Publication No. H5-105424. A coating liquid containing magnesium fluoride particles is coated on a carrier to form a film on the carrier. However, the film obtained by this method has a drawback of very low mechanical strength and poor adhesion to the carrier.

Therefore, development of an antireflection film having a good refractive index, good mechanical strength, good adhesion to a carrier, and low manufacturing cost is an extremely desirable target in the field.

The present invention provides an antireflective coating composition which can produce an antireflection film having a good refractive index, good mechanical strength, good adhesion to a carrier, and low manufacturing cost.

The present invention provides an antireflective coating composition comprising 0.7 wt% to 2 wt% of ceria microparticles, 0.1 wt% to 1.1 wt% of a niobate compound, 0.05 wt% to 20 wt% of water, 79 wt % to 99 wt% of an organic solvent and an anion, wherein in the antireflective coating composition, the concentration of the anion ranges from more than 85.1 ppm to less than 132.4 ppm.

In one embodiment of the present invention, the cerium oxide microparticles include at least a compound obtained by hydrolysis-condensation reaction of an alkoxydecane represented by the formula (I) in the presence of a basic catalyst: R _n -Si ( OR1) _4-n Formula (I), wherein in the formula (I), R is a substituted or unsubstituted alkyl group of C1 to C10, a substituted or unsubstituted alkenyl group of C2 to C10 or C6~ A substituted or unsubstituted aryl group of C10, R1 is a substituted or unsubstituted alkyl group of C1 to C10, and n is an integer of 0-2.

In one embodiment of the present invention, the alkaline catalyst is selected from the group consisting of metal hydroxides, ammonia water, alkylamines, alcohol amines, benzyltriethylammonium chloride, and tetramethylammonium hydroxide. At least one of the ethnic groups.

In one embodiment of the present invention, the above-described tellurite compound includes at least a compound obtained by hydrolysis-condensation reaction of an alkoxydecane represented by the formula (I) in the presence of an acidic catalyst: R _n -Si (OR1) _4-n Formula (I) wherein, in the formula (I), R is a substituted or unsubstituted alkyl group of C1 to C10, a substituted or unsubstituted alkenyl group of C2 to C10 or a C6~C10 The substituted or unsubstituted aryl group, R1 is a substituted or unsubstituted alkyl group of C1 to C10, and n is an integer of 0-2.

In one embodiment of the present invention, the acidic catalyst is selected from the group consisting of hydrochloric acid, nitric acid, hydrofluoric acid, acetic acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, boric acid, formic acid, oxalic acid, p-toluenesulfonic acid, and alkylsulfonic acid. At least one of the group consisting of.

In one embodiment of the present invention, when n is 0, the alkoxydecane represented by the above formula (I) includes tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane or tetrabutoxy Base alkane; when n is 1, the alkoxydecane represented by the above formula (I) includes methyltrimethoxydecane, methyltriethoxydecane, methyltriphenoxydecane, ethyltrimethoxy Base decane, ethyl triethoxy decane, propyl trimethoxy decane, propyl triethoxy decane, butyl trimethoxy decane, butyl triethoxy decane, hexyl trimethoxy decane, octyl trimethyl Oxydecane, mercaptotrimethoxydecane, γ-(2-aminoethyl)aminopropyltrimethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, γ-epoxypropane Oxypropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-chloropropyltrimethoxydecane, vinyltrimethoxydecane or phenyltrimethoxydecane; when n is 2, the above The alkoxydecane represented by the formula (I) includes dimethyldimethoxydecane, dimethyldiethoxydecane, diisopropyldimethoxydecane, diisobutylene. Dimethoxydecane, cyclohexylmethyldimethoxydecane, γ-chloropropylmethyldimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, γ-glycidoxypropyl Methyl dimethoxy decane or γ-methyl propylene methoxy propyl methyl dimethoxy decane.

In an embodiment of the invention, in the above formula (I), n is 0 or 1.

In an embodiment of the invention, the content ratio of the cerium oxide microparticles to the citrate compound is from 5:5 to 7:3.

In one embodiment of the present invention, the anion is selected from the group consisting of chloride ions, nitrate ions, fluoride ions, acetate ions, trifluoroacetate ions, sulfate ions, phosphate ions, borate ions, formate ions, At least one of the group consisting of an oxalate ion, a p-toluenesulfonate ion, and an alkylsulfonate ion.

The present invention further provides an antireflective coating composition comprising 0.7 wt% to 2 wt% of ceria microparticles, 0.1 wt% to 1.1 wt% of a niobate compound, 0.05 wt% to 20 wt% of water, 79 A wt% to 99 wt% organic solvent and an anion, wherein in the antireflective coating composition, the anion has a molar concentration ranging from greater than 2.13 mM to less than 3.32 mM.

In an embodiment of the invention, the content ratio of the cerium oxide microparticles to the citrate compound is from 5:5 to 7:3.

In one embodiment of the present invention, the anion is selected from the group consisting of chloride ions, nitrate ions, fluoride ions, acetate ions, trifluoroacetate ions, sulfate ions, phosphate ions, borate ions, formate ions, At least one of the group consisting of an oxalate ion, a p-toluenesulfonate ion, and an alkylsulfonate ion.

The antireflection film of the present invention is produced from the above antireflective coating composition.

In an embodiment of the invention, the antireflection film has a refractive index of 1.3 to 1.48.

Based on the above, the antireflective coating composition proposed by the present invention comprises 0.7 wt% to 2 wt% of ceria microparticles, 0.1 wt% to 1.1 wt% of a niobate compound, and 0.05 wt% to 20 wt% of water. 79% to 99% by weight of the organic solvent and an anion in the antireflective coating composition having a concentration ranging from greater than 85.1 ppm to less than 132.4 ppm or an anion having a molar concentration ranging from greater than 2.13 mM to less than 3.32 mM, such that The antireflection film prepared therefrom can simultaneously have a good refractive index, mechanical strength, adhesion to a carrier, and transmittance.

The above described features and advantages of the present invention will be more apparent from the following description.

In the present specification, the range represented by "a value to another value" is a schematic representation that avoids enumerating all the values in the range in the specification. Therefore, the recitation of a particular range of values is intended to include any value in the range of values and the range of values defined by any value in the range of values, as in the specification. The scope is the same.

Herein, if a group is not indicated to be substituted, the group may represent a substituted or unsubstituted group. For example, "alkyl" can mean a substituted or unsubstituted alkyl group. Further, when a group crown is described by "C _X ", it means that the main chain of the group has X carbon atoms.

In order to prepare an antireflection film having a good refractive index, good mechanical strength, good adhesion to a carrier, and low manufacturing cost, the present invention proposes an antireflective coating composition which can attain the above advantages. Hereinafter, an embodiment will be specifically described as an example in which the present invention can be implemented.

An antireflective coating composition provided by an embodiment of the present invention includes 0.7 wt% to 2 wt% of ceria microparticles, 0.1 wt% to 1.1 wt% of a niobate compound, 0.05 wt% to 20 wt% of water, 79 wt% to 99 wt% of an organic solvent and an anion, wherein in the antireflective coating composition, the concentration of the anion ranges from more than 85.1 ppm to less than 132.4 ppm, preferably from 87 ppm to 120 ppm, most preferably from 88 ppm to 93 ppm. Further, in the present embodiment, the content ratio of the cerium oxide microparticles to the citrate compound may be from 5:5 to 7:3. In the present embodiment, the density of the antireflective coating composition is, for example, 0.89 g/cm ³ .

In an embodiment of the invention, the anion is, for example, selected from the group consisting of chloride ions, nitrate ions, fluoride ions, acetate ions, trifluoroacetate ions, sulfate ions, phosphate ions, borate ions, formate ions, At least one of a group consisting of an oxalate ion, a p-toluenesulfonate ion, and an alkylsulfonate ion, and preferably a chloride ion, a nitrate ion, an acetate ion, a sulfate ion, a phosphate ion, or an oxalate ion Or an alkyl sulfonate ion.

Further, in the present embodiment, the antireflective coating composition is an alkoxy decane represented by the following formula (I) in the presence of water and an organic solvent, respectively, in an alkaline catalyst and an acid catalyst. a mixture of a cerium oxide microparticle-containing dispersion obtained by a hydrolytic condensation reaction and a cerium-containing compound-containing solution: R _n -Si(OR1) _{4-n is a} formula (I), wherein in the formula (I), R is a substituted or unsubstituted alkyl group of C1 to C10, a substituted or unsubstituted alkenyl group of C2 to C10 or a substituted or unsubstituted aryl group of C6 to C10, and R1 is a C1 to C10 The substituted or unsubstituted alkyl group, n is an integer from 0 to 2. From another point of view, in the present embodiment, the cerium oxide microparticles include at least a hydrolysis condensation reaction of the alkoxydecane represented by the above formula (I) in the presence of water, an organic solvent and an alkaline catalyst. And the phthalate compound includes at least a compound obtained by hydrolysis-condensation reaction of the alkoxydecane represented by the above formula (I) in the presence of water, an organic solvent and an acidic catalyst. That is, in the present embodiment, an alkoxydecane for reacting to form ceria granules in the presence of a basic catalyst and an alkoxy decane for reacting to form a phthalate compound in the presence of an acid catalyst Compared with alkoxydecane which can be used in the presence of an alkaline catalyst to react to form cerium oxide microparticles in the presence of an alkaline catalyst, which can have the same or different chemical formulas Most preferred are alkoxydecanes of the formula (I) wherein n is 0. Further, the alkoxy group in the alkoxydecane represented by the formula (I) is a hydrolyzable group, that is, a group which can undergo a hydrolysis reaction and is bonded to hydrazine.

It is worth mentioning that, as described above, the dispersion containing cerium oxide microparticles is alkaline and the solution containing the citrate compound is acidic, so acid is generated in order to avoid the formation of the antireflective coating composition when the solutions are mixed to form an antireflective coating composition. The alkali is neutralized to produce a large amount of undesired salts. In the present embodiment, the dispersion containing the cerium oxide microparticles may be passed through a cation exchange resin to control the pH of the mixture to 2.5 before the solution is mixed. Between 5.5.

Specifically, in the definition of R, alkyl includes, but is not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, and alkenyl includes, but not limited to, vinyl or Allyl, and aryl includes, but is not limited to, phenyl, styryl or anilino; in the definition of R1, alkyl includes, but is not limited to, methyl, ethyl, propyl, butyl, pentyl, Hexyl, heptyl or octyl. Further, in the definition of R and R1, the substituent includes, but is not limited to, an amino group, an alkylamino group, a (meth)acryloxy group, a glycidoxy group, a decyl group or a halogen group, wherein the alkylamino group is, for example, an amine. The ethylamino group, the halogen group is, for example, a chlorine group.

In formula (I), when n is 2, a plurality of R may be the same or different; and when n represents 0, 1, or 2, a plurality of R1 may be the same or different.

Further, when n is 0, the alkoxydecane represented by the formula (I) is a tetrafunctional alkoxydecane, and includes, for example but not limited to, tetramethoxydecane, tetraethoxydecane, tetrapropoxy. a decane or a tetrabutoxy decane; when n is 1, the alkoxy decane of the formula (I) is a trifunctional alkoxy decane, for example but not limited to: methyltrimethoxynonane, methyl three Ethoxy decane, methyltriphenoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, propyltrimethoxydecane, propyltriethoxydecane, butyltrimethoxydecane, Butyl triethoxydecane, hexyltrimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane, γ-(2-aminoethyl)aminopropyltrimethoxydecane, γ-甲Acryloxypropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-chloropropyltrimethoxydecane, vinyltrimethoxy a decyl alkane, a phenyl trimethoxy decane; and when n is 2, the alkoxy decane of the formula (I) is a difunctional alkoxy decane, for example including but not Limited to: dimethyl dimethoxy decane, dimethyl diethoxy decane, diisopropyl dimethoxy decane, diisobutyl dimethoxy decane, cyclohexyl methyl dimethoxy decane, Γ-chloropropylmethyldimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, γ-glycidoxypropylmethyldimethoxydecane or γ-methylpropene oxime Propyl propyl dimethoxy decane.

In the present embodiment, n is preferably 0 or 1 in the formula (I) based on the retention of mechanical strength. Specifically, the alkoxydecane represented by the formula (I) is preferably tetraethoxydecane, tetramethoxydecane, γ-glycidoxypropyltrimethoxydecane, methyltrimethoxydecane. , γ-methacryloxypropyltrimethoxydecane.

In the present embodiment, the basic catalyst is, for example, a metal hydroxide such as sodium hydroxide or potassium hydroxide; ammonia water; methylamine, n-propylamine, n-butylamine, dimethylamine, trimethylamine, diethylamine, and triethylamine. An alkylamine such as an amine, tripropylamine, dibutylamine, tributylamine, hexylamine or octylamine; an alcoholamine such as diethanolamine or triethanolamine; benzyltriethylammonium chloride; or tetramethylammonium hydroxide.

In the present embodiment, as the acidic catalyst, both inorganic acids and organic acids are suitable, wherein the inorganic acid is, for example, hydrochloric acid, nitric acid, hydrofluoric acid, acetic acid, trifluoroacetic acid, sulfuric acid, phosphoric acid or boric acid; and the organic acid is, for example, formic acid. , acetic acid, oxalic acid, p-toluenesulfonic acid or alkylsulfonic acid.

It is worth mentioning that in the present embodiment, the anion is, for example, a product derived from hydrolysis of an acidic catalyst, and is preferably a chloride ion.

In the present embodiment, the type of the organic solvent is not particularly limited as long as each component can be effectively dissolved or dispersed without precipitation. Specific examples of the organic solvent include alcoholic solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl cellosolve, ethylene glycol, and butanol; ethyl acetate and butyl acetate; An ester solvent such as an ester; a ketone solvent such as acetone or methyl ethyl ketone; an aromatic solvent such as toluene or xylene; or a guanamine solvent such as dimethylformamide or dimethylacetamide. The above organic solvents may be used singly or in combination as long as the components can be effectively dissolved or dispersed without precipitation.

Further, in the present embodiment, the dispersion liquid containing cerium oxide microparticles is obtained by subjecting a liquid to an alkoxy group in the presence of water and an organic solvent by a hydrolysis and condensation reaction using an alkoxy decane under an alkaline catalyst. The molar ratio of decane is 25 to 55:1, preferably 30 to 45:1; the molar ratio of the basic catalyst to the alkoxydecane is 0.1 to 2.0:1, preferably 0.3 to 1.2:1; The molar ratio of water to alkoxydecane is from 1.5 to 8:1, preferably from 2.5 to 6:1.

In the present embodiment, the reaction temperature of the dispersion containing cerium oxide microparticles is 40 ° C to 100 ° C, preferably 55 ° C to 90 ° C; and the reaction time is 30 minutes to 4 hours, preferably 1 hour to 3 hours. .

In the present embodiment, the solution containing a phthalate compound is obtained by subjecting a solution of alkoxy decane to an acid catalyst under hydrolysis and condensation in the presence of water and an organic solvent, wherein the organic solvent and the alkoxydecane are in a molar state. The ratio is 5 to 15:1, preferably 7 to 12:1; the molar ratio of the acidic catalyst to the alkoxydecane is 0.007 to 0.014:1, preferably 0.009 to 0.012:1; water and alkoxy group. The molar ratio of decane is from 1.5 to 8:1, preferably from 2.5 to 6:1.

In the present embodiment, the reaction temperature of the solution containing the citrate compound is from 30 ° C to 100 ° C, preferably from 45 ° C to 100 ° C; and the reaction time is from 30 minutes to 5 hours, preferably from 2 hours to 3.5 hours.

Another embodiment of the present invention provides an antireflective coating composition comprising 0.7 wt% to 2 wt% of ceria microparticles, 0.1 wt% to 1.1 wt% of a niobate compound, and 0.05 wt% to 20 wt% of water. , 79 wt% to 99 wt% of an organic solvent and an anion, wherein in the antireflective coating composition, the molar concentration of the anion ranges from greater than 2.13 millimolar (mM) to less than 3.32 millimolar (mM). Preferably, it is from 2.18 millimolar (mM) to 3.0 millimolar (mM), most preferably from 2.21 millimolar (mM) to 2.33 millimolar (mM). It is to be noted that the related description of the components in the anti-reflective coating composition of the present embodiment has been described in detail in the above embodiments, and thus will not be described herein.

Another embodiment of the present invention provides an antireflection film produced by any of the antireflective coating compositions of any of the foregoing embodiments. In detail, the refractive index of the anti-reflection film is, for example, between 1.3 and 1.48, and preferably between 1.38 and 1.47. Further, the transmittance of the antireflection film is, for example, greater than or equal to 93% at a wavelength of 550 nm.

It is worth mentioning that, as described above, the components in the anti-reflective coating composition include cerium oxide microparticles, phthalate compounds, water, organic solvents, and anions, and each component has a specific content range, thereby The anti-reflective film produced has good refractive index and transmittance, good mechanical strength and good adhesion to the carrier.

Further, in the present embodiment, the antireflection film is prepared, for example, by applying an antireflective coating composition onto a substrate and then performing a drying treatment. Specifically, the method of applying the antireflective coating composition can be carried out by a coating method generally performed, such as a dip coating method, a spin coating method, a spray coating method, a brush coating method, a roll transfer method, or a screen printing method. , inkjet or offset printing. The substrate may be a glass substrate or an acrylic substrate. The drying treatment method is, for example, heating using a hot plate or a hot air circulating oven, wherein the temperature condition is 90 to 180 ° C, for example, 100 ° C to 180 ° C, and the time condition is 5 to 60 minutes, for example, 7 to 45. minute.

It is worth mentioning that since the anti-reflection film does not need to use a special process (such as vacuum process such as evaporation or sputtering), it can be obtained by a simple process (ie, coating and heating process). Easy to manufacture and low in manufacturing cost.

The features of the present invention will be more specifically described below with reference to Examples 1 to 3 and Comparative Examples 1 and 2. Although the following Examples 1 to 3 are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the invention. Therefore, the invention should not be construed restrictively by the examples described below. Preparation of dispersion containing cerium oxide microparticles

In a three-necked flask having a volume of 500 ml, 311 parts by weight of ethanol, 6.93 parts by weight of pure water, and 19 parts by weight of aqueous ammonia (29%) were added, and the mixture was stirred at room temperature for 10 minutes to uniformly mix. Next, 31.26 parts by weight of tetraethoxysilane was added, and the three-necked flask was immersed in an oil bath at 60 ° C and stirred for 3 hours to obtain a basic dispersion of cerium oxide-containing fine particles. Thereafter, the alkaline cerium oxide-containing fine particle-containing dispersion was passed through a cation exchange resin (product name: SK1BH, manufacturer: Taiyang Chemical Co., Ltd.) to control its pH to 4.56 to obtain A dispersion of cerium oxide microparticles, wherein the cerium oxide microparticles have a solid content of 3% and a particle size distribution of 20 nm to 70 nm.

Further, 10 uL of the dispersion containing the cerium oxide microparticles was taken, and after 1000-fold dilution, the type and concentration of anions were measured by an ion chromatograph (DIOEX, model: ICS 1500). The measurement showed that no anions were detected. Preparation of a solution containing a phthalate compound

In a three-necked flask having a volume of 500 ml, 52.1 parts by weight of tetraethoxydecane and 103.66 parts by weight of ethanol were added, and 18.7 parts by weight of an aqueous hydrochloric acid solution (0.6 weight) was added thereto over 30 minutes while stirring at room temperature. A portion of a mixed aqueous solution of 35% hydrochloric acid and 18.1 parts by weight of deionized water). Next, the three-necked flask was immersed in an oil bath at 60 ° C and stirred for 2 hours to obtain a solution containing a phthalate compound having a solid content of 11.5% and a particle size distribution of 10 nm to 90. Nm.

Further, 10 uL of the solution containing the phthalate compound was taken and diluted 1000 times, and the type and concentration of anions were measured by an ion chromatograph (DIOEX, model: ICS 1500). The measurement results showed that the chloride ion concentration was 1725 ppm, and the other anions were not detected, so the anion concentration of the solution containing the citrate compound was 1725 ppm. Example 1

80 parts by weight of the dispersion containing cerium oxide fine particles was mixed with 20.87 parts by weight of a solution containing a phthalate compound, and the mixture was stirred at room temperature for 3 hours to obtain an antireflective coating composition of Example 1. The content of each component in the antireflective coating composition of Example 1 is shown in Table 1.

Next, the antireflective coating composition of Example 1 was applied by spin coating on a glass substrate (product name: Corning EXG glass, manufacturer: Sharpon Optoelectronics). Thereafter, the glass substrate was placed in an oven and baked at a temperature of 160 ° C for 10 minutes to obtain an antireflection film of Example 1, wherein the film thickness was 101.8 nm. Example 2

75 parts by weight of the dispersion containing cerium oxide fine particles was mixed with 13.04 parts by weight of a solution containing a phthalate compound, and then stirred at room temperature for 3 hours to obtain an antireflective coating composition of Example 2. The content of each component in the antireflective coating composition of Example 2 is shown in Table 1.

Next, the antireflective coating composition of Example 2 was applied by spin coating on a glass substrate (product name: Corning EXG glass, manufacturer: Sharpon Optoelectronics). Thereafter, the glass substrate was placed in an oven and baked at a temperature of 150 ° C for 20 minutes to obtain an antireflection film of Example 2, wherein the film thickness was 98.4 nm. Example 3

After 100 parts by weight of the dispersion containing cerium oxide fine particles was mixed with 11.18 parts by weight of a solution containing a phthalate compound, the mixture was stirred at room temperature for 3 hours to obtain an antireflective coating composition of Example 3. The content of each component in the antireflective coating composition of Example 3 is shown in Table 1.

Next, the antireflective coating composition of Example 3 was applied by spin coating on a glass substrate (product name: Corning EXG glass, manufacturer: Sharpon Optoelectronics). Thereafter, the glass substrate was placed in an oven and baked at a temperature of 160 ° C for 20 minutes to obtain an antireflection film of Example 3, in which the film thickness was 100.5 nm. Comparative example 1

After 40 parts by weight of the dispersion containing cerium oxide fine particles and 24.35 parts by weight of a solution containing a ceric acid compound, the mixture was stirred at room temperature for 3 hours to obtain an antireflective coating composition of Comparative Example 1. The content of each component in the antireflective coating composition of Comparative Example 1 is shown in Table 1.

Next, the antireflective coating composition of Comparative Example 1 was applied by spin coating on a glass substrate (product name: Corning EXG Glass, manufacturer: Sharpon Optoelectronics). Thereafter, the glass substrate was placed in an oven and baked at a temperature of 120 ° C for 30 minutes to obtain an antireflection film of Comparative Example 1, in which the film thickness was 97.9 nm. Comparative example 2

After 85 parts by weight of the dispersion containing cerium oxide fine particles was mixed with 5.54 parts by weight of a solution containing a ceric acid compound, the mixture was stirred at room temperature for 3 hours to obtain an antireflective coating composition of Comparative Example 2. The content of each component in the antireflective coating composition of Comparative Example 2 is shown in Table 1.

Next, the antireflective coating composition of Comparative Example 2 was applied by spin coating on a glass substrate (product name: Corning EXG glass, manufacturer: Sharp Optoelectronics). Thereafter, the glass substrate was placed in an oven and baked at a temperature of 150 ° C for 10 minutes to obtain an antireflection film of Comparative Example 2, in which the film thickness was 97.7 nm.

Hereinafter, the antireflective coating composition of Examples 1 to 3 and the antireflection film thereof, and the antireflective coating composition of Comparative Examples 1 to 2 and the antireflection film thereof were tested for each of the enumerated physical properties. The evaluation, and the principles of each test are detailed below, and the results of each test are shown in Table 1. < anion concentration >

The anti-reflective coating composition of Example 1 to Example 3 and Comparative Example 1 to Comparative Example 2 was respectively subjected to 10 uL, and after 1000-fold dilution, an anion species was carried out by an ion chromatograph (DIOEX, model: ICS 1500). And the measurement of the concentration. In addition, since only the chloride ions were detected in the antireflective coating compositions of Examples 1 to 3 and Comparative Examples 1 to 2, and other kinds of anions were not detected, the conditions in Table 1 were The anion concentration is the chloride ion concentration. < anionic molar concentration >

First, 10 uL of the antireflective coating composition of Example 1 to Example 3 and Comparative Example 1 to Comparative Example 2 were respectively taken, and anion was carried out by ion chromatography (DIOEX, Model: ICS 1500) after 1000-fold dilution. The type and concentration measurement. Then, since only the chloride ions were detected in the antireflective coating compositions of Examples 1 to 3 and Comparative Examples 1 to 2, the molecular weight of the chloride ions was 35.5 g/mol and the antireflective coating composition was used. The density was 0.89 g/cm ³ for concentration conversion. It is also noted that the anion molar concentration in Table 1 is the chloride ion molar concentration. < pencil hardness >

The surface of the antireflection film of Examples 1 to 3 and the antireflection film of Comparative Example 1 to Comparative Example 2 were each subjected to hardness measurement in accordance with the pencil hardness test of JIS K5600-5-4. Generally, the pencil hardness specification of the antireflection film is preferably greater than or equal to 5H, more preferably greater than or equal to 6H. < Hundreds of adhesion test >

First, the antireflective coating compositions of Examples 1 to 3 and Comparative Examples 1 to 2 were respectively applied by spin coating to a glass substrate of 10 cm × 10 cm (product name: Corning EXG glass, manufactured). Merchant: Ruilong Optoelectronics). Thereafter, the glass substrate was placed in an oven and baked according to the baking conditions described in the above Examples 1 to 3 and Comparative Examples 1 and 2 to obtain Example 1 having a size of 10 cm × 10 cm. The antireflection film of Example 3 and the antireflection film of Comparative Example 1 to Comparative Example 2. Next, according to the method of JIS K5600, the antireflection film of the above-mentioned Examples 1 to 3 and the antireflection film of Comparative Example 1 to Comparative Example 2 were respectively cut into 10 squares × 10 by a cutter. 100 squares. After that, the 600 tape manufactured by 3M Company was adhered to the printing surface, and then peeled off sharply, and the number of remaining squares was evaluated. The evaluation criteria were as follows: 5B: no square peeling off; 4B: 0% < shedding The number of squares is 5%; 3B: 5% < the number of squares falling off ≦ 15%; 2B: 15% < the number of squares falling off ≦ 35%; 1B: 35% < the number of squares falling off ≦ 65%; 0B: 65% < the number of squares dropped off ≦ 100%. < Permeability test >

The antireflection films of Examples 1 to 3 and the antireflection films of Comparative Examples 1 to 2 were measured for the wavelength range of 380 nm to 780 nm using a UV/Vis spectrometer (Hitachi, Model: U3300), respectively. Transmittance (%). Here, in Table 1, the transmittance (%) (550 nm) represents the transmittance (%) at a wavelength of 550 nm. Generally, the antireflection film has a transmittance of at least 93% at a wavelength of 550 nm. < refractive index test >

The antireflection films of Examples 1 to 3 and the antireflection films of Comparative Examples 1 to 2 were measured at a wavelength of 550 nm using a film measuring instrument (Mission Peak Optics Inc., model: MP100-ST). The refractive index underneath. Generally, the antireflection film has a refractive index of at least less than 1.5, preferably between 1.3 and 1.45. Table 1         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Example 1 </td><td> Example 2 < /td><td> Example 3 </td><td> Comparative Example 1 </td><td> Comparative Example 2 </td></tr><tr><td> Antireflective Coating Composition</ Td><td> cerium oxide microparticles (wt%) </td><td> 1% </td><td> 1.2% </td><td> 1.4% </td><td> 0.6% < /td><td> 1.6% </td></tr><tr><td> citrate compound (wt%) </td><td> 1% </td><td> 0.8% </ Td><td> 0.6% </td><td> 1.4% </td><td> 0.4% </td></tr><tr><td> water (wt%) </td><td > 10% </td><td> 10% </td><td> 10% </td><td> 10% </td><td> 10% </td></tr><tr> <td> Ethanol (wt%) </td><td> 88% </td><td> 88% </td><td> 88% </td><td> 88% </td><td > 88% </td></tr><tr><td> Anion concentration (ppm) </td><td> 106.7 </td><td> 94.2 </td><td> 90.5 </td> <td> 132.4 </td><td> 85.1 </td></tr><tr><td> Anion molar concentration (mM) </td><td> 2.68 </td><td> 2.36 < /td><td> 2.27 </td><td> 3.32 </td><td> 2.13 </td></tr><tr><td> Content ratio of cerium oxide microparticles to citrate compound /td><td> 5:5 </td><td> 6:4 </t d><td> 7:3 </td><td> 3:7 </td><td> 8:2 </td></tr><tr><td> Anti-reflective film properties</td> <td> pencil hardness</td><td> 7H </td><td> 7H </td><td> ≦7H </td><td> ≦5H </td><td> 5H </td ></tr><tr><td> Hundreds of tests</td><td> 5B </td><td> 5B </td><td> 5B </td><td> 5B </td> <td> 4B </td></tr><tr><td> Transmittance (%) (550 nm) </td><td> 93.4 </td><td> 93.4 </td><td > 93.9 </td><td> 93.5 </td><td> 94.7 </td></tr><tr><td> Refractive Index</td><td> 1.396 </td><td> 1.392 </td><td> 1.385 </td><td> 1.434 </td><td> 1.430 </td></tr></TBODY></TABLE>

As is apparent from the above Table 1, the pencil hardness of the antireflection films of Examples 1 to 3 was all greater than or equal to 7H, which shows that the antireflection films of Examples 1 to 3 have good mechanical strength. In addition, as can be seen from the above Table 1, the evaluation results of the hundred-dimensional test of the antireflection films of Examples 1 to 3 were all 5B, which showed that the antireflection film of Examples 1 to 3 had a good relationship with the substrate. Adhesion. Further, as is apparent from the above Table 1, the transmittances of the antireflection films of Examples 1 to 3 were all greater than 93% (93.4%, 93.9%) at a wavelength of 550 nm. This shows the results of Examples 1 to 3. The antireflection film has a good transmittance. Further, the antireflection films of Examples 1 to 3 all had lower refractive indices (1.385 to 1.396) than the antireflection films of Comparative Examples 1 to 2, which shows Examples 1 to 3. The antireflection film has better antireflection ability. That is, the antireflection films of Examples 1 to 3 obtained from the antireflective coating compositions of Examples 1 to 3 simultaneously have good mechanical strength, adhesion to the carrier, and penetration. Rate and refractive index.

In summary, the anti-reflective coating composition proposed by the present invention comprises 0.7 wt% to 2 wt% of ceria microparticles, 0.1 wt% to 1.1 wt% of a niobate compound, and 0.05 wt% to 20 wt%. Water, 79 wt% to 99 wt% organic solvent, and anions in the antireflective coating composition having a concentration ranging from greater than 85.1 ppm to less than 132.4 ppm or an anion having a molar concentration ranging from greater than 2.13 mM to less than 3.32 mM Therefore, the antireflection film prepared therefrom can simultaneously have good refractive index, mechanical strength, adhesion to the carrier, and transmittance. Further, since the antireflection film is prepared by using the antireflective coating composition of the present invention, it can be produced without using a special process (for example, a vacuum process such as evaporation or sputtering), so that it is extremely easy to manufacture and inexpensive to manufacture.

The present invention has been disclosed in the above embodiments, but it is not intended to limit the invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

no.

no.

no.

Claims (14)

An antireflective coating composition comprising: 0.7 wt% to 2 wt% of cerium oxide microparticles; 0.1 wt% to 1.1 wt% of a citrate compound; 0.05 wt% to 20 wt% of water; 79 wt% to 99 a wt% organic solvent; and an anion, wherein in the antireflective coating composition, the concentration of the anion ranges from greater than 85.1 ppm to less than 132.4 ppm. The anti-reflective coating composition according to claim 1, wherein the cerium oxide microparticles comprise at least a hydrolyzed condensation reaction of an alkoxydecane represented by the formula (I) in the presence of a basic catalyst. a compound: R _n -Si(OR1) _{4-n is a} formula (I) wherein, in the formula (I), R is a substituted or unsubstituted alkyl group of C1 to C10, and a substituted or non-substituted C2 to C10 group. A substituted alkenyl group or a substituted or unsubstituted aryl group of C6-C10, R1 is a substituted or unsubstituted alkyl group of C1 to C10, and n is an integer of 0-2. The anti-reflective coating composition according to claim 2, wherein the basic catalyst is selected from the group consisting of metal hydroxides, ammonia water, alkylamines, alcohol amines, benzyltriethylammonium chloride, and At least one of the group consisting of tetramethylammonium hydroxide. The anti-reflective coating composition according to claim 1, wherein the bismuth citrate compound comprises at least a hydrolysis condensation reaction of an alkoxy decane represented by the formula (I) in the presence of an acidic catalyst. Compound: R _n -Si(OR1) _4-n Formula (I) wherein, in the formula (I), R is a substituted or unsubstituted alkyl group of C1 to C10, a substituted or non-substituted C2~C10 a substituted alkenyl group or a substituted or unsubstituted aryl group of C6 to C10, R1 is a substituted or unsubstituted alkyl group of C1 to C10, and n is an integer of 0-2. The antireflective coating composition according to claim 4, wherein the acidic catalyst is selected from the group consisting of hydrochloric acid, nitric acid, hydrofluoric acid, acetic acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, boric acid, formic acid, acetic acid, oxalic acid. At least one of the group consisting of p-toluenesulfonic acid and alkylsulfonic acid. The antireflective coating composition according to Item 2 or 4, wherein when a n is 0, the alkoxydecane represented by the formula (I) includes tetramethoxynonane, tetraethoxydecane. , tetrapropoxydecane or tetrabutoxydecane; when n is 1, the alkoxydecane represented by the formula (I) includes methyltrimethoxydecane, methyltriethoxydecane, methyltriphenyl Oxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, propyltrimethoxydecane, propyltriethoxydecane, butyltrimethoxydecane, butyltriethoxydecane, hexyl Trimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane, γ-(2-aminoethyl)aminopropyltrimethoxydecane, γ-methylpropenyloxypropyltrimethoxy Baseline, γ-glycidoxypropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-chloropropyltrimethoxydecane, vinyltrimethoxydecane or phenyltrimethoxydecane When n is 2, the alkoxydecane represented by the formula (I) includes dimethyldimethoxydecane, dimethyldiethoxydecane, diisopropyldimethoxyanthracene. , diisobutyldimethoxydecane, cyclohexylmethyldimethoxydecane, γ-chloropropylmethyldimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, γ-ring Oxypropoxypropylmethyldimethoxydecane or gamma-methacryloxypropylmethyldimethoxydecane. The antireflective coating composition according to claim 2, wherein in the formula (I), n is 0 or 1. The antireflective coating composition according to claim 1, wherein the content ratio of the cerium oxide microparticles to the citrate compound is from 5:5 to 7:3. The antireflective coating composition of claim 1, wherein the anion is selected from the group consisting of chloride ions, nitrate ions, fluoride ions, acetate ions, trifluoroacetate ions, sulfate ions, and phosphate ions. At least one of a group consisting of borate ions, formate ions, oxalate ions, p-toluenesulfonate ions, and alkylsulfonate ions. An antireflective coating composition comprising: 0.7 wt% to 2 wt% of cerium oxide microparticles; 0.1 wt% to 1.1 wt% of a citrate compound; 0.05 wt% to 20 wt% of water; 79 wt% to 99 a wt% organic solvent; and an anion, wherein the anion has a molar concentration ranging from greater than 2.13 mM to less than 3.32 mM in the antireflective coating composition. The antireflective coating composition according to claim 10, wherein the content ratio of the cerium oxide microparticles to the citrate compound is from 5:5 to 7:3. The antireflective coating composition according to claim 10, wherein the anion is selected from the group consisting of chloride ion, nitrate ion, fluoride ion, acetate ion, trifluoroacetate ion, sulfate ion, and phosphate ion. At least one of a group consisting of borate ions, formate ions, oxalate ions, p-toluenesulfonate ions, and alkylsulfonate ions. An antireflection film produced by the antireflective coating composition according to any one of claims 1 to 12. The antireflection film of claim 13, wherein the antireflection film has a refractive index of from 1.3 to 1.48.