Resin composition for anti-reflective coating, anti-reflective coating, and solid-state image sensor

Abstract

The present invention provides a resin composition for an anti-reflective coating, an anti-reflective coating formed from the composition, and a solid-state image sensor containing the anti-reflective coating, comprising hollow aluminosilicate particles, a binder resin, a solvent, and an additive, wherein the hollow aluminosilicate particles have a Si / Al molar ratio of 7 to 15 and their surface is modified with a silane compound or non-reactive resin of a specific structure, and the additive comprises a phosphoric acid-based dispersant. [Effects] The resin composition for anti-reflective coatings according to the present invention exhibits a low refractive index, suppresses crack formation during coating, has excellent coating film flatness, prevents particle aggregation and foreign matter generation, prevents moisture adsorption under high temperature and high humidity conditions, prevents moisture permeation by developing and stripping solutions, and also exhibits excellent particle size change stability and sedimentation stability.

Description

[Technical Field]

[0001] The present invention relates to a resin composition for anti-reflective coatings, an anti-reflective coating, and a solid-state image sensor, and more specifically, to a resin composition for anti-reflective coatings, an anti-reflective coating, and a solid-state image sensor that exhibit a low refractive index, suppress the occurrence of cracks during coating film formation, have excellent coating film flatness, prevent particle aggregation and foreign matter generation, prevent moisture adsorption under high temperature and high humidity conditions, prevent moisture permeation by developing and stripping solutions, and also exhibit excellent particle size change stability and sedimentation stability. [Background technology]

[0002] A solid-state image sensor is an element that converts images captured by light energy into electrical information. It has a photoelectric conversion element on which a light-gathering microlens is provided, and an anti-reflective coating is formed on its surface. Such an anti-reflective coating plays a role in preventing noise such as flare and ghosting.

[0003] Anti-reflective coatings applied to solid-state image sensors require fine and highly precise processing and molding capabilities. Therefore, conventionally, vapor-phase methods such as vacuum deposition and sputtering, which are suitable for microfabrication, have been employed.

[0004] However, vapor phase methods such as vacuum deposition and sputtering have the problem of high manufacturing costs due to the expensive equipment required.

[0005] Therefore, a coating method has been proposed in which a composition capable of forming an anti-reflective film is applied to a substrate and cured, as an alternative to the vapor phase method.

[0006] For example, Korean Published Patent No. 10-2010-0123610 discloses a method for forming an anti-reflective film by applying a coating solution containing hollow silica particles and a binder resin as low refractive index particles.

[0007] However, conventional anti-reflective coating compositions using hollow silica particles have problems such as cracking during film formation, reduced film flatness, moisture adsorption under high temperature and high humidity conditions, and moisture permeation by developers and strippers.

[0008] Furthermore, untreated hollow silica particles have a hydrophilic surface, which causes them to absorb moisture from the air, leading to aggregation between particles and reduced fluidity. Additionally, poor miscibility with polymeric substances and organic solvents in the composition can lead to the generation of foreign matter, potentially causing a decline in quality.

[0009] Furthermore, when the dispersibility of inorganic particles such as hollow silica particles decreases, their aggregation causes changes in particle size and leads to sedimentation, which presents a problem in ensuring stability over time.

[0010] Therefore, there is a need for the development of a resin composition for anti-reflective coatings that exhibits a low refractive index, suppresses crack formation during coating film formation, has excellent coating film flatness, prevents particle aggregation and foreign matter generation, prevents moisture adsorption under high temperature and high humidity conditions, prevents moisture permeation by developing and stripping solutions, and also exhibits excellent particle size change stability and sedimentation stability. [Overview of the project] [Problems that the invention aims to solve]

[0011] One objective of the present invention is to provide a resin composition for anti-reflective coatings that exhibits a low refractive index, suppresses crack formation during coating film formation, has excellent coating film flatness, prevents particle aggregation and foreign matter generation, prevents moisture adsorption under high temperature and high humidity conditions, prevents moisture permeation by developing and stripping solutions, and also exhibits excellent particle size change stability and sedimentation stability.

[0012] Another object of the present invention is to provide an anti-reflective film formed using the resin composition for anti-reflective films.

[0013] Another object of the present invention is to provide a solid-state image sensor equipped with the anti-reflective coating. [Means for solving the problem]

[0014] On the other hand, the present invention comprises hollow aluminosilicate particles, a binder resin, a solvent, and an additive. The hollow aluminosilicate particles have a Si / Al molar ratio of 7 to 15, and their surface is modified with a compound represented by the following chemical formula 1 or a non-reactive resin. The aforementioned additive provides a resin composition for anti-reflective coatings, which includes a phosphate-based dispersant.

[0015] [ka]

[0016] In the above formula, R 1 C1-C 20 It is an alkyl group, R 2 ~R 4 These are each an independent C1-C4 alkoxy group.

[0017] In one embodiment of the present invention, the average particle size of the hollow aluminosilicate particles may be 30 to 150 nm.

[0018] In one embodiment of the present invention, the non-reactive resin may contain repeating units represented by the following chemical formula 2.

[0019] [ka]

[0020] In the above formula, R 5 is a hydrogen atom or a methyl group, L 1 It does not exist, or C1-C 10 alkylene group or C1-C 10which is an oxyalkylene group, R 6 is a hydroxy group, a C1-C4 alkoxy group or a halogen, and R 7 is a hydrogen atom or C1-C 20 alkyl group, and n is an integer of 1 to 3.

[0021] In one embodiment of the present invention, the phosphate-based dispersant may have an acid value of 20 to 150 mg KOH / g.

[0022] In one embodiment of the present invention, the phosphate-based dispersant may be included in an amount of 0.01 to 10% by weight based on 100% by weight of the total solid content in the resin composition for an antireflection film.

[0023] The resin composition for an antireflection film according to one embodiment of the present invention may further comprise amorphous silica particles.

[0024] The resin composition for an antireflection film according to one embodiment of the present invention may satisfy the following Mathematical Formula 1. [Mathematical Formula 1] 1≦a / b≦15 In the above formula, a is the average particle diameter of hollow aluminosilicate particles, and b is the average particle diameter of amorphous silica particles.

[0025] In one embodiment of the present invention, a cured film formed from the resin composition for an antireflection film may have a refractive index of 1.10 to 1.35 at 550 nm.

[0026] In another aspect, the present invention provides an antireflection film formed using the resin composition for an antireflection film.

[0027] In still another aspect, the present invention provides a solid-state imaging device comprising the antireflection film.

Effects of the Invention

[0028] The resin composition for anti-reflective coatings according to the present invention exhibits a low refractive index, suppresses crack formation during coating, has excellent coating film flatness, prevents particle aggregation and foreign matter generation, prevents moisture adsorption under high temperature and high humidity conditions, prevents moisture permeation by developing and stripping solutions, and also exhibits excellent particle size change stability and sedimentation stability. Therefore, the resin composition for anti-reflective coatings according to the present invention can be advantageously applied to anti-reflective coatings for solid-state image sensors. [Modes for carrying out the invention]

[0029] The present invention will be described in more detail below.

[0030] One embodiment of the present invention comprises hollow aluminosilicate particles (A), a binder resin (C), a solvent (D), and an additive (E). The hollow aluminosilicate particles have a Si / Al molar ratio of 7 to 15, and their surface is modified with a compound represented by the following chemical formula 1 or a non-reactive resin. The aforementioned additive relates to a resin composition for anti-reflective coatings, comprising a phosphate-based dispersant.

[0031] [ka]

[0032] In the above formula, R 1 C1-C 20 It is an alkyl group, R 2 ~R 4 These are each an independent C1-C4 alkoxy group.

[0033] The Si / Al molar ratio refers to the molar ratio of silicon (Si) element in the hollow aluminosilicate particles to the aluminum (Al) element used for modification.

[0034] The Si / Al molar ratio is 7 to 15, preferably 7 to 12, and more preferably 8 to 12, as described above. If the Si / Al molar ratio is below the above range, the aluminum content increases, and a complete hollow structure may not be formed due to the formation of micropores on the shell surface. As a result, the strength of the hollow particles decreases, and high-density hollow particles cannot be produced. Furthermore, if the Si / Al molar ratio is below the above range, there is aluminum that has not dissolved into the shell, which may increase the refractive index and cause particle aggregation. On the other hand, if the Si / Al molar ratio exceeds the above range, when forming micropores in the shell, not only the aluminum on the shell surface but also the core particles cannot be completely removed, which increases the refractive index and makes it difficult to maintain the hollow shape in the hydrothermal reaction.

[0035] In one embodiment of the present invention, the cured film formed from the anti-reflective resin composition may have a refractive index of 1.10 to 1.35, preferably 1.10 or more and less than 1.25, at 550 nm.

[0036] By controlling the refractive index at 550 nm of the cured film formed from the anti-reflective resin composition to within the aforementioned range, it is possible to improve the light-gathering efficiency of the solid-state image sensor by eliminating noise such as flare and ghosting, as the film is located above the high-refractive-index layer exhibiting a refractive index of 1.60 or higher.

[0037] [Hollow aluminosilicate particles (A)] In one embodiment of the present invention, the hollow aluminosilicate particles (A) play a role in reducing the refractive index while maintaining the strength of the coating film, thereby improving the anti-reflective properties.

[0038] The hollow aluminosilicate particles (A) are Al-modified silica particles, with a Si / Al molar ratio of 7 to 15, preferably 7 to 12, and more preferably 8 to 12.

[0039] By modifying the hollow aluminosilicate particles (A) with Al, they can achieve a low degree of cohesion, excellent dispersibility, and high density in a hydrothermal reaction.

[0040] The hollow aluminosilicate particles can be obtained by first producing core-shell particles in which an aluminosilicate shell is formed by reacting a silane compound and an aluminum (Al) precursor with a template core consisting of an organic polymer micelle or reverse micelle, and then reacting the core-shell particles with a basic aqueous solution or an acidic aqueous solution to form fine pores in the shell, while simultaneously removing the core. If necessary, the hollow aluminosilicate particles can be further subjected to a hydrothermal reaction to increase their density.

[0041] The organic polymers that form the micelles or reverse micelles are amphoteric polymers that are both hydrophobic and hydrophilic, and may include, for example, polyoxyethylene taloamine, polyoxyethylene oleylamine, polyoxyethylene sterylamine, polyoxyethylene laurylamine, polyoxyethylene sorbitan ester, and polyoxyethylene octyl ether. These organic polymers may be used individually or in combination of two or more.

[0042] The organic polymer forms micelles or reverse micelles in a solvent. The type of solvent is not particularly limited and may be selected and used according to the properties of the organic polymer. Specifically, the solvent may be an alcohol, a glycol ester, a ketone, or a mixture thereof. The alcohol may be methanol, ethanol, isopropanol, etc., the glycol ester may be methyl cellosolve, ethyl cellosolve, etc., and the ketone may be methyl ethyl ketone, methyl isobutyl ketone, etc.

[0043] The silane compound can be readily bonded to the organic polymer that forms the template core. Such bonding may be carried out by the Stober method (Werner, 1968). During the sol-gel process of shell production using the Stober method, a stable shell can be produced by hydrolysis and condensation polymerization synthesis using an acidic or basic solution contained in the solvent.

[0044] The silane compound may be any and all, including alkoxysilanes, chlorosilanes, and bromosilanes. For example, the silane compound may be tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-(meth)acrylooxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylchlorosilane, trimethylbromosilane, etc. These silane compounds may be used individually or in combination of two or more.

[0045] The type of aluminum precursor is not particularly limited, and for example, an organic salt or alkoxide of aluminum may be used.

[0046] The silane compound and aluminum precursor combine with the core material to form an aluminosilicate shell, thereby producing core-shell particles. The produced core-shell particles can be reacted with a basic aqueous solution or an acidic aqueous solution to form micropores in the shell. These micropores facilitate the entry and exit of dissolved organic polymers. As a result, the organic polymers inside the shell can be easily removed through a simple washing step.

[0047] The basic aqueous solution may be sodium hydroxide, ammonium hydroxide, potassium hydroxide, phosphate hydroxide, or a mixture thereof, and the acidic aqueous solution may be hydrochloric acid, nitric acid, sulfuric acid, acetic acid, or a mixture thereof.

[0048] As the washing solvent, distilled water, alcohol, glycol, glycol ester, or a mixture thereof may be used. As the alcohol, methanol, ethanol, isopropanol, etc. may be used, as the glycol, ethylene glycol, propylene glycol, etc. may be used, and as the glycol ester, ethyl cellosolve, methyl cellosolve, etc. may be used.

[0049] The hydrothermal reaction may be carried out at a temperature of 160 to 250°C.

[0050] In one embodiment of the present invention, the average particle size of the hollow aluminosilicate particles may be 30 to 150 nm, preferably 40 to 120 nm, and more preferably 50 to 90 nm. When the average particle size of the hollow aluminosilicate particles is within the above range, it is easier to control it to satisfy the mathematical formula 1 described later, and the refractive index of the cured film can be controlled more effectively. If the average particle size of the hollow aluminosilicate particles is less than the above range, the volume of air within the hollow aluminosilicate particles decreases, making it difficult to lower the refractive index, and the thin shell thickness can make them prone to crumbling, making it difficult to maintain the hollow shape. If the average particle size of the hollow aluminosilicate particles exceeds the above range, the flatness of the coating film decreases, and differences in refractive index may occur even within the coating film.

[0051] The hollow aluminosilicate particles are modified on their surface with a compound represented by the following chemical formula 1 or a non-reactive resin.

[0052] [ka]

[0053] In the above formula, R 1 C1-C 20 It is an alkyl group, R 2 ~R 4These are each an independent C1-C4 alkoxy group.

[0054] C1-C used in this specification 20 The alkyl group refers to a linear or branched hydrocarbon consisting of 1 to 20 carbon atoms, and includes, but is not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, 2-ethylheptyl, octyl, nonyl, decyl, undecyl, todecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl, nonadecyl, and eicosanyl.

[0055] As used herein, the C1-C4 alkoxy group refers to a linear or branched alkoxy group consisting of 1 to 4 carbon atoms, and includes, but is not limited to, methoxy, ethoxy, n-propanoxy, and others.

[0056] The compound represented by chemical formula 1 plays a role in preventing the aggregation of silicate particles due to the non-reactive alkyl group.

[0057] If the compound used for surface modification is a reactive compound, aggregation of hollow aluminosilicate particles may occur, inhibiting dispersion stability. Furthermore, aggregated particles may appear as foreign matter during coating film formation, resulting in poor coating film flatness, as well as poor moisture permeability at high temperatures and high humidity, and poor moisture permeability by the developer and stripper.

[0058] In one embodiment of the present invention, R 1 Preferably C1-C 15 Alkyl alkyl groups, more preferably C1-C 10 Alkyl alkyl groups, more preferably C2-C 10 It may be an alkyl group. 1 If the chain length is long, steric hindrance can prevent aggregation of hollow aluminosilicate particles and improve dispersibility. However, R 1If the chain length is too long, the compatibility with polymeric substances and organic solvents in the composition decreases, leading to particle precipitation and Kellification, resulting in poor storage stability. Furthermore, high-temperature, high-humidity moisture permeability and moisture permeability by developers and strippers may also be poor. 1 When the chain length is within the aforementioned preferred range, the dispersion is excellent, particle aggregation during coating film formation is suppressed, and the flatness of the coating film is excellent.

[0059] The non-reactive resin may contain repeating units represented by the following chemical formula 2.

[0060] [ka]

[0061] In the above formula, R 5 is a hydrogen atom or a methyl group, L 1 It does not exist, or C1-C 10 alkylene group or C1-C 10 It is an oxyalkylene group, R 6 These are a hydroxyl group, a C1-C4 alkoxy group, or a halogen. R 7 is a hydrogen atom or C1-C 20 It is an alkyl group, n is an integer between 1 and 3.

[0062] C1-C used in this specification 10 The alkylene group refers to a linear or branched divalent hydrocarbon consisting of 1 to 10 carbon atoms, and includes, but is not limited to, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, and n-norylene.

[0063] C1-C used in this specification 10The oxyalkylene group refers to a functional group in which one or more carbon atoms in a linear or branched divalent hydrocarbon consisting of 1 to 10 carbon atoms are replaced by oxygen. Examples include, but are not limited to, oxymethylene, oxyethylene, oxypropylene, oxybutylene, oxypentylene, and oxyhexylene.

[0064] The non-reactive resin may further contain repeating units represented by the following chemical formula 3.

[0065] [ka]

[0066] In the above formula, R 8 is a hydrogen atom or a methyl group, L 2 It does not exist, or C1-C 18 It is an alkylene group.

[0067] C1-C used in this specification 18 The alkylene group refers to a linear or branched divalent hydrocarbon consisting of 1 to 18 carbon atoms, and includes, but is not limited to, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, and n-norylene.

[0068] Preferably, L 2 It may either not exist or be a C1-C6 alkylene group.

[0069] In one embodiment of the present invention, the repeating unit represented by chemical formula 2 may be included in an amount of 30 to 99 mol%, preferably 50 to 95 mol%, and more preferably 60 to 90 mol%, relative to 100 mol% of the total repeating units constituting the non-reactive resin. When the repeating unit represented by chemical formula 2 is included within the above mol% range, the reactivity with silanol groups (Si-OH) on the silica surface is high, and the efficiency of surface modification can be increased.

[0070] In one embodiment of the present invention, the repeating unit represented by chemical formula 3 may be present in an amount of 1 to 70 mol%, preferably 5 to 50 mol%, and more preferably 10 to 40 mol%, relative to 100 mol% of the total repeating units constituting the nonreactive resin. When the repeating unit represented by chemical formula 3 is present within the above mol% range, it is preferable because, for example, the pH can be adjusted to promote hydrolysis of the alkoxy group.

[0071] The non-reactive resin may further contain other repeating units in addition to the repeating units represented by chemical formulas 2 to 3.

[0072] The non-reactive resin may be a block copolymer in which the repeating units represented by chemical formulas 2 to 3 are repeated in a constant manner, or a random copolymer in which these are repeated randomly.

[0073] The method for producing the non-reactive resin is not particularly limited, and a method well known in the art may be used.

[0074] The non-reactive resin may have a polystyrene-equivalent weight-average molecular weight (hereinafter simply referred to as "weight-average molecular weight") of 3,000 to 8,000, as measured by gel permeation chromatography (GPC; using tetrahydrofuran as the eluent). A weight-average molecular weight within this range of the non-reactive resin is preferable because it results in excellent hydrophobicity of the modified surface.

[0075] The surface modification of the hollow aluminosilicate particles may be carried out by hydrolyzing the compound represented by chemical formula 1 or a non-reactive resin to form silanol (-Si-OH) groups, and then reacting them with the hollow aluminosilicate particles.

[0076] The hollow aluminosilicate particles may be present in an amount of 10 to 98% by weight, preferably 40 to 90% by weight, based on 100% by weight of the total solids in the resin composition for the anti-reflective coating. If amorphous silica particles, described later, are further present, the hollow aluminosilicate particles may be present in an amount of 20 to 80% by weight, preferably 35 to 70% by weight, based on 100% by weight of the total solids in the resin composition for the anti-reflective coating. If the amount of hollow aluminosilicate particles is less than the above-mentioned range, the low refractive index effect cannot be observed, and the anti-reflective coating cannot function. If the amount exceeds the above-mentioned range, the formation of the coating film is not easy.

[0077] [Binder resin (C)] In one embodiment of the present invention, the binder resin (C) is reactive in response to heat and performs the function of a binder resin.

[0078] Furthermore, the binder resin (C) has excellent moisture resistance and chemical resistance in high-temperature and high-humidity environments, which helps prevent the refractive index from increasing and thus reducing the anti-reflective efficiency.

[0079] In one embodiment of the present invention, the binder resin is not particularly limited as long as it is a thermosetting resin.

[0080] For example, a siloxane resin may be used as the binder resin.

[0081] A commercially available product may be used as the siloxane resin.

[0082] Furthermore, a polysiloxane compound may be used as the binder resin.

[0083] The polysiloxane compound may include a hydrolysis condensate of a silane compound represented by the following chemical formula 4. [Chemical formula 4] R 9 m Si(OR 10 ) 4-m In the above formula, R 9 C1-C 20 These are alkyl groups, vinyl groups, aryl groups, or aralkyl groups. R 10 is a C1-C4 alkyl group, m is an integer between 0 and 3.

[0084] The aryl groups used herein include all aromatic groups, heteroaromatic groups, and their partially reduced derivatives. The aromatic groups are monocyclic or fusion rings with 5 to 15 members, and the heteroaromatic groups are aromatic groups containing one or more oxygen, sulfur, or nitrogen atoms. Representative examples of aryl groups include, but are not limited to, phenyl, naphthyl, pyridinyl, pyrimidinyl, pyrrolyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolyl, oxazolyl, thiazolyl, and tetrahydronaphthyl.

[0085] As used herein, the aralkyl group refers to a complex group formed by the substitution of an aryl group (aromatic hydrocarbon group) on the carbon of an alkyl group, and includes, but is not limited to, benzyl and phenethyl.

[0086] As used herein, C1-C4 alkyl groups refer to linear or branched monovalent hydrocarbons consisting of 1 to 4 carbon atoms, and include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and t-butyl.

[0087] In one embodiment of the present invention, the polysiloxane compound may include a hydrolysis condensate of a mixture of silane compounds represented by the following chemical formulas 4-1 to 4-4, in terms of improving crosslinkability, thereby increasing the degree of hardening, and improving the reliability of the coating film. [Chemical formula 4-1] Si(OR 10 )4 [Chemical formula 4-2] R 9 Si(OR 10 )3 [Chemical formula 4-3] R 9 2Si(OR 10 )2 [Chemical formula 4-4] R 9 3Si(OR 10 ) In the above formula, R 9 C1-C 20 These are alkyl groups, vinyl groups, aryl groups, or aralkyl groups. R 10 It is a C1-C4 alkyl group.

[0088] Examples of silane compounds represented by the chemical formula 4-1 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane.

[0089] Examples of silane compounds represented by the chemical formula 4-2 include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

[0090] Examples of silane compounds represented by chemical formula 4-3 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, benzylmethyldimethoxysilane, and benzylmethyldiethoxysilane.

[0091] Examples of silane compounds represented by the chemical formula 4-4 include trimethylmethoxysilane, triethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, benzyldimethylmethoxysilane, and benzyldimethylethoxysilane.

[0092] The mixing ratio of the silane compounds represented by the chemical formulas 4-1 to 4-4 may be 1:1.5 to 2.5:2.5 to 3.5:3.5 to 4.5, preferably 1:1.7 to 2.3:2.7 to 3.3:3.7 to 4.3, and more preferably 1:1.9 to 2.1:2.9 to 3.1:3.9 to 4.1, in terms of molar basis, from the perspective of adjusting the degree of crosslinking of the polysiloxane.

[0093] The polysiloxane compound may be produced by a hydrosol-gel reaction of the silane compound represented by chemical formula 4.

[0094] Specifically, the alkoxy group of the silane compound represented by chemical formula 4, which is the starting material, is hydrolyzed with water to form a hydroxyl group, which then condenses with the alkoxy group or hydroxyl group of another silane compound represented by chemical formula 4 to form a siloxane bond, thereby forming a polysiloxane.

[0095] To accelerate the sol-gel reaction, a catalyst may preferably be added. Suitable catalysts include acid catalysts such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, chlorosulfonic acid, p-tolueneic acid, trichloroacetic acid, polyphosphate, pyrophosphate, iodic acid, tartaric acid, and perchloric acid; base catalysts such as ammonia, sodium hydroxide, n-butylamine, di-n-butylamine, tri-n-butylamine, imidazole, ammonium perchlorate, potassium hydroxide, and barium hydroxide; and ion exchange resins such as Amberite IPA-400(Cl). The amount of catalyst used is not particularly limited, and 0.0001 to 10 parts by weight may be added per 100 parts by weight of the silane compound.

[0096] The aforementioned sol-gel reaction may be carried out with stirring at room temperature for 6 to 144 hours, or it may be carried out at 60 to 80°C for 4 to 36 hours to accelerate the reaction rate and ensure complete condensation.

[0097] Furthermore, the binder resin may be one which has thermosetting functional groups such as hydroxyl groups, epoxy groups, or oxetane groups in its molecule.

[0098] For example, the binder resin having the thermosetting functional group may contain one or more repeating units represented by the following chemical formulas 5 to 9.

[0099] [ka] JPEG2026145006000008.jpg48169

[0100] In the above formula, R11 ~R 16 Each of these is independently a hydrogen atom or a methyl group, L 3 ~L 6 They either do not exist independently, or C1-C 10 alkylene group or C1-C 10 It is an oxyalkylene group, R 17 This is a residue containing a hydrogen atom or a carboxylic acid derived from an acid anhydride.

[0101] The acid anhydrides used herein include succinic anhydride, methylsuccinic anhydride, (2-dodecen-1-yl)succinic anhydride, phenylsuccinic anhydride, phthalic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, 3,3-dimethylglutaric anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and trimellitic anhydride. This includes, but is not limited to, anhydrides, hexahydrophthalic anhydride, and carbic anhydride. From the standpoint of ease of reaction, it is preferable to use maleic anhydride, phthalic anhydride, trimellitic anhydride, succinic anhydride, hexahydrophthalic anhydride and / or carbic anhydride as the acid anhydride, and trimellitic anhydride, succinic anhydride and / or hexahydrophthalic anhydride are particularly preferred.

[0102] The binder resin having the thermosetting functional group may further contain other repeating units in addition to the repeating units.

[0103] For example, the binder resin having the thermosetting functional group may further contain repeating units derived from an ethylenically unsaturated monomer having a carboxyl group.

[0104] Specific examples of ethylenically unsaturated monomers having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; and mono(meth)acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate. Among these, acrylic acid and methacrylic acid are preferred.

[0105] Furthermore, the binder resin having the thermosetting functional group may further contain repeating units derived from other monomers having unsaturated double bonds.

[0106] Specific examples of monomers having the aforementioned unsaturated double bond include: Hydroxyalkyl (meth)acrylate compounds such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate; Aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, and p-vinylbenzylglycidyl ether; N-substituted maleimide compounds such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Alkyl (meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, N-butyl (meth)acrylate, i-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; Alicyclic (meth)acrylate compounds such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 2-dicyclopentanyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate; Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; Unsaturated oxetane compounds such as 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, and 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Examples include vinyl cyanide compounds such as (meth)acrylonitrile and α-chloroacrylonitrile. These may be used individually or in combination of two or more.

[0107] The method for producing the binder resin having the thermosetting functional group is not particularly limited, and a method well known in the art may be used.

[0108] The binder resin may be present in an amount of 1 to 89% by weight, preferably 5 to 55% by weight, based on 100% by weight of the total solids in the resin composition for the anti-reflective film. If amorphous silica particles, described later, are further present, the binder resin may be present in an amount of 1 to 50% by weight, preferably 5 to 30% by weight, based on 100% by weight of the total solids in the resin composition for the anti-reflective film. When the binder resin satisfies the above range, it can maintain stability even at high temperatures and have high resistance to various chemical substances, improving chemical resistance and corrosion resistance. If the binder resin is present in an amount less than the above content range, adhesion to the substrate and chemical resistance may be poor due to insufficient curing, and if it is present in an amount exceeding the above content range, the particle content may relatively decrease and the refractive index may increase.

[0109] [Solvent (D)] The solvent (D) is not particularly limited, and various organic solvents used in the art may be used.

[0110] Specific examples of the solvent (D) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate; and alkylene glycol alkyl ethers such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate. Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, and propylene glycol ethyl propyl ether; propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate; butyl diol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, and butoxybutyl alcohol;Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxyacetate, and butoxybutyl acetate; butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, and butoxybutyl propionate; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methyl ethyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin;Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxy Butyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-propionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Examples include esters such as 3-ethyl 3-ethoxypropionate propyl, 3-ethoxypropionate butyl, 3-propoxypropionate methyl, 3-propoxypropionate ethyl, 3-propoxypropionate propyl, 3-propoxypropionate butyl, 3-butoxypropionate methyl, 3-butoxypropionate ethyl, 3-butoxypropionate propyl, and 3-butoxypropionate butyl; cyclic ethers such as tetrahydrofuran and pyran; and cyclic esters such as γ-butyrolactone. The solvents (D) exemplified here may be used individually or in combination of two or more.

[0111] The solvent (D) may preferably be an ester such as diethylene glycol dialkyl ethers, alkylene glycol alkyl ether acetates, ketones, butanediol monoalkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate, considering its applicability and drying properties. More preferably, it may be diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate.

[0112] The solvent may be present in an amount of 90 to 97% by weight relative to 100% by weight of the entire resin composition for the anti-reflective coating. It is preferable that the solvent content be within the above range because it results in good coatability when applied using coating equipment such as a spin coater, slit and spin coater, slit coater (sometimes also called a die coater or curtain flow coater), or inkjet printer.

[0113] [Additive (E)] In one embodiment of the present invention, the additive (E) includes a phosphate-based dispersant.

[0114] The aforementioned phosphate-based dispersant improves the dispersibility of hollow aluminosilicate particles and amorphous silica particles (described later) to prevent their sedimentation, and also reduces the surface tension of the resin composition for the anti-reflective coating to improve coating properties.

[0115] The phosphate-based dispersant may include those having an ester group in the molecule, i.e., phosphate ester-based dispersants. The phosphate-based dispersant may include forms in which the hydroxyl group or the hydrogen atom of the hydroxyl group present in the phosphate ester ((HO)2PO(OR)) or phosphoric acid (H3PO4) is substituted with another functional group or is not substituted.

[0116] In particular, the phosphate-based dispersant may contain an ester group and a polyether residue and / or a polyester residue within its molecule.

[0117] In the present invention, "poly-" refers to a compound consisting of multiple repeating units, and the "polyether residue" and "polyester residue" may refer to residues consisting of 1 to 20 repeating units, each containing an ether group and an ester group, respectively. Preferably, in the present invention, the repeating units may consist of 5 to 20, and more preferably 10 to 20.

[0118] In one embodiment of the present invention, the phosphate-based dispersant may have an acid value of 20 to 150 mg KOH / g.

[0119] When the acid value is within the aforementioned range, the phosphate-based dispersant is effective in uniformly dispersing the particles. If the acid value falls outside this range, it may actually decrease the dispersion stability. In other words, when the acid value is appropriate, the phosphate-based dispersant is more easily adsorbed onto the surface of the particles, preventing aggregation between particles and helping to maintain uniform dispersion even during long-term storage.

[0120] Examples of the phosphate-based dispersants include Disperbyk-110 and 111, and they may be used alone or in combination of two or more.

[0121] The phosphate-based dispersant may have a molecular weight of 1,000 to 4,000.

[0122] The phosphate-based dispersant may be present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on 100% by weight of the total solids in the resin composition for the anti-reflective coating. If the phosphate-based dispersant is present in an amount less than the above content range, the particles are more likely to aggregate and form clumps or precipitate in the solution, which can consequently impede the uniformity of the dispersion. If the phosphate-based dispersant is present in an amount exceeding the above content range, it may actually reduce the stability of the dispersion system. This is because the dispersant acts excessively on the surface of the particles, inducing aggregation between the particles.

[0123] In one embodiment of the present invention, the additive (E) may further include a leveling agent.

[0124] The leveling agent may be a commercially available surfactant, such as silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, or amphoteric surfactants. These may be used individually or in combination of two or more.

[0125] Examples of the aforementioned silicone-based surfactants include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicone Co., Ltd., and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 from GE Toshiba Silicone Co., Ltd. Examples of the aforementioned fluorine-based surfactants include commercially available products such as Megafac F-470, F-471, F-475, F-482, F-489, and F-554 from Dainippon Ink and Chemicals, Inc.

[0126] The leveling agent may be included in an amount of 0.0001 to 0.01% by weight based on 100% by weight of the total anti-reflective coating resin composition. It is preferable that the content of the leveling agent be within the above range, as this results in excellent film-forming properties of the anti-reflective coating resin composition and good flatness of the coating film formed from the composition.

[0127] The resin composition for anti-reflective coatings according to one embodiment of the present invention may further contain, as necessary, additives such as a curing agent, a slip-improving agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-coagulation agent, a radical generator, and a photoacid generator, in addition to the components described above.

[0128] The curing agent is used to enhance deep curing and mechanical strength. Specific examples of curing agents include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

[0129] Specific examples of epoxy compounds in the curing agent include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac-type epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic, or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxidized products, isoprene (co)polymer epoxidized products, glycidyl (meth)acrylate (co)polymers, triglycidyl isocyanurates, and the like.

[0130] Specific examples of oxetane compounds in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

[0131] The curing agent may be used in combination with a curing aid compound that enables ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing aid compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators.

[0132] The polycarboxylic acid anhydrides mentioned above may be commercially available epoxy resin curing agents. Examples of epoxy resin curing agents include trade names such as (ADEKA Hardener EH-700) (manufactured by ADEKA Corporation), (Ricacid HH) (manufactured by Shin-Nippon Rika Co., Ltd.), and (MH-700) (manufactured by Shin-Nippon Rika Co., Ltd.). The curing agents exemplified above may be used individually or in mixtures of two or more.

[0133] Examples of the aforementioned slip-improving agents include commercially available products such as BYK-333 (manufactured by BYK).

[0134] As the adhesion promoter, silane compounds are preferred. Specifically, examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatetopropyltriethoxysilane.

[0135] The aforementioned antioxidants include, specifically, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra- tert-butyldibenz[d,f][1,3,2]dioxaphosfepine, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis(6-tert-butyl-4-methylphenol),4,4'-butylidenebis(6-tert-butyl-3-methylphenol) (L), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityltetrakis(3-laurylthiopropionate), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy) Examples include cybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],2,6-di-tert-butyl-4-methylphenol, etc.

[0136] Examples of the aforementioned ultraviolet absorbers include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

[0137] Examples of the aforementioned anti-coagulation agent include sodium polyacrylate.

[0138] Examples of the aforementioned radical generators include commercially available products such as OXE 01 (manufactured by BASF).

[0139] Examples of commercially available photoacid generators include Irgacure 290 (manufactured by BASF).

[0140] The resin composition for anti-reflective coating according to one embodiment of the present invention may further contain amorphous silica particles (B).

[0141] [Amorphous silica particles (B)] In one embodiment of the present invention, the amorphous silica particles (B) play a role in suppressing crack formation while maintaining the strength of the coating film and improving the flatness of the coating film.

[0142] The amorphous silica particles (B) are silica particles that do not have a hollow space inside their structure and lack any regularity in their particle shape.

[0143] The amorphous silica particles (B) may be commercially available and used.

[0144] For example, the amorphous silica particles (B) include, but are not limited to, MT-10, DM-10, DM-30, DM-20S, DM-30S, KS-20SC, HG-09, HM-20L, HM-30S, ZD-30ST, PM-09, PM-20, X-20, and X-30 (manufactured by Tokuyama Corporation).

[0145] In one embodiment of the present invention, the average particle size of the amorphous silica particles may be 7 to 25 nm, preferably 7 to 22 nm, and more preferably 12 to 22 nm. When the average particle size of the amorphous silica particles is within this range, it is easier to control it to satisfy mathematical formula 1 described later, and the refractive index of the cured film can be controlled more effectively. If the average particle size of the amorphous silica particles is below this range, gelation of the particles during storage may not be suppressed, and if it exceeds this range, the refractive index increases, the surface roughness of the coating film increases, and haze may occur.

[0146] The amorphous silica particles may be present in the resin composition for the anti-reflective coating in an amount of 70% by weight or less, for example, 10 to 70% by weight, preferably 20 to 50% by weight, relative to 100% by weight of the total solids. When the amorphous silica particles are present within this content range, they are sufficiently embedded between the hollow aluminosilicate particles in the coating film, and the surface roughness of the coating film can be reduced. If the amorphous silica particles are present in an amount exceeding 70% by weight, the content of hollow aluminosilicate particles decreases relatively, which may make it difficult to lower the refractive index.

[0147] The resin composition for anti-reflective coating according to one embodiment of the present invention may satisfy the following mathematical formula 1. [Mathematical formula 1] 1 ≤ a / b ≤ 15 In the above formula, a is the average particle size of hollow aluminosilicate particles, and b is the average particle size of amorphous silica particles.

[0148] The a / b value is the average particle size ratio of hollow aluminosilicate particles to amorphous silica particles, and is 1 to 15, preferably 1 to 13, and more preferably 1.8 to 12.5, as shown in mathematical formula 1. If the a / b value is less than the above range, the refractive index may increase due to the large particle size amorphous silica particles, and the amorphous silica particles may not be sufficiently embedded between the hollow aluminosilicate particles, resulting in a decrease in the flatness of the coating film. If it exceeds the above range, the flatness of the coating film may decrease due to the large particle size hollow aluminosilicate particles.

[0149] One embodiment of the present invention relates to an anti-reflective film formed using the above-described resin composition for anti-reflective films.

[0150] According to the present invention, the anti-reflective film may be manufactured by applying the above-described resin composition for anti-reflective films onto a substrate and then applying heat.

[0151] A preferred example of the manufacturing process is to apply the anti-reflective resin composition onto a substrate, and then heat-dry it to remove volatile components such as solvents and obtain a smooth coating.

[0152] Coating methods include, for example, spin coating, casting, roll coating, slit and spin coating, or slit coating.

[0153] After coating, the coating is heated and dried (pre-baked), or heated after vacuum drying to volatilize volatile components such as solvents. Here, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C.

[0154] Next, exposure and development steps may be performed as needed.

[0155] Finally, the process proceeds to another heating step (post-bake) to form a hardened network. Here, the heating temperature is usually around 70 to 230°C. A hot plate, clean oven, or infrared heater may be used as the heating method. Note that this invention does not limit the heating method.

[0156] Using the resin composition for anti-reflective coatings according to the present invention, a cured film can be formed on a substrate through the above-described steps.

[0157] The cured film obtained in this way can be usefully used as an anti-reflective coating for solid-state image sensors.

[0158] The thickness of the cured film may be 50 to 700 nm.

[0159] Therefore, one embodiment of the present invention relates to a solid-state image sensor equipped with the anti-reflective coating described above.

[0160] The solid-state image sensor may include, for example, a CCD (Charged Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor) image sensor.

[0161] The solid-state image sensor includes a support containing a semiconductor element or a photoelectric conversion element and a microlens, and the anti-reflective coating may be formed on the microlens.

[0162] The present invention will be described in more detail below with reference to examples, comparative examples, and experimental examples. It should be noted that these examples, comparative examples, and experimental examples are merely for illustrative purposes, and it will be obvious to those skilled in the art that the scope of the present invention is not limited thereto.

[0163] [Synthesis Example 1: Production of Non-Reactive Resin] A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube was prepared. Next, a polymerizable mixture containing 91.2 g (0.35 mol, 70 mol%) of 3-diethoxymethylsilylpropyl methacrylate and 12.9 g (0.15 mol, 30 mol%) of methacrylic acid was prepared.

[0164] Next, 4 g of t-butylperoxy-2-ethyl exanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added to the polymerizable mixture and stirred to prepare a monomer solution. A mixed solution of 6 g of n-dodecanethiol and 24 g of PGMEA was then prepared as a chain transfer agent.

[0165] Next, 395 g of PGMEA was introduced into the flask, the atmosphere inside the flask was switched from air to nitrogen, and the temperature of the flask was raised to 70°C while stirring. The monomer solution and the chain transfer agent were added dropwise to the flask via a dropping funnel over a period of 2 hours while maintaining a temperature of 70°C.

[0166] After 1 hour, the temperature was raised to 75°C and maintained for 12 hours, after which bubbling of an oxygen / nitrogen 5 / 95 (v / v) mixed gas was started through a gas inlet tube. Subsequently, 0.4 g of 2,2'-methylenebis(4-methyl-6-t-butylphenol) and 0.8 g of triethylamine were added to the flask and reacted at 70°C for 8 hours to obtain unreactive resin 1.

[0167] The acid value of the solid content of the resin synthesized in this way was 92.3 mgKOH / g, and the weight-average molecular weight Mw, measured by GPC, was approximately 4,500.

[0168] [Synthesis Example 2: Production of Non-Reactive Resin] Non-reactive resin 2 was obtained in the same manner as in Synthesis Example 1, except that 3-methacryloxypropyl triethoxysilane was used instead of 3-diethoxymethylsilylpropyl methacrylate.

[0169] The acid value of the solid content of the resin synthesized in this way was 97.3 mgKOH / g, and the weight-average molecular weight Mw, measured by GPC, was approximately 5,500.

[0170] [Manufacturing Example 1-1: Manufacturing of Hollow Aluminosilicate Particles (A-1)] 0.172 g of polyacrylic acid, 0.086 g of polystyrene sulfonic acid, and 3 ml of ammonium hydroxide were placed in a 1 L three-necked round-bottom flask, and then 60 ml of ethanol was added to prepare a core template for the hollow structure. While stirring the solution, 8 ml of 3% aluminum isopropoxide and 60 ml of ethanol containing tetraethoxysilane were added using a syringe pump to obtain spherical particles containing the core. These particles were reacted with 5% sodium hydroxide, then washed with distilled water and alcohol, and dried to produce aluminosilicate particles with a hollow structure. 20 g of the produced particles and 80 g of distilled water were placed in an ultrasonic disperser and ultrasonically dispersed for 1 hour to produce a stable aqueous dispersion of aluminosilicate. This dispersion was placed in a 1 L hydrothermal reactor and reacted at 180°C for 10 hours, after which it was precipitated and dried to produce hollow aluminosilicate particles with increased shell density. A dispersion of aluminosilicate propylene glycol monomethyl ether acetate with a solid content of 10% by weight was prepared by substituting the solvent with propylene glycol monomethyl ether acetate. The average particle size was 78 nm, and the Si / Al molar ratio was 12.

[0171] [Manufacturing Example 1-2: Manufacturing of Hollow Aluminosilicate Particles (A-2)] A dispersion of hollow aluminosilicate particles was obtained in the same manner as in Preparation Example 1-1, except that 10 ml of 3% aluminum isopropoxide was used. The average particle size was 40 nm, and the Si / Al molar ratio was 10.

[0172] [Manufacturing Example 1-3: Manufacturing of Hollow Aluminosilicate Particles (A-3)] A dispersion of hollow aluminosilicate particles was obtained in the same manner as in Preparation Example 1-1, except that 12 ml of 3% aluminum isopropoxide was used. The average particle size was 150 nm, and the Si / Al molar ratio was 8.

[0173] [Manufacturing Example 1-4: Manufacturing of Hollow Aluminosilicate Particles (A-4)] A dispersion of hollow aluminosilicate particles was obtained in the same manner as in Preparation Example 1-1, except that 6 ml of 3% aluminum isopropoxide was used. The average particle size was 74 nm, and the Si / Al molar ratio was 16.

[0174] [Manufacturing Example 1-5: Manufacturing of Hollow Aluminosilicate Particles (A-5)] A dispersion of hollow aluminosilicate particles was obtained in the same manner as in Preparation Example 1-1, except that 20 ml of 3% aluminum isopropoxide was used. The average particle size was 74 nm, and the Si / Al molar ratio was 5.

[0175] [Manufacturing Example 2-1: Manufacturing of surface-modified hollow aluminosilicate particles (F-1)] Surface-modified hollow aluminosilicate particles were produced by applying the method described in the paper Korean Chem. Eng. Res., Vol. 49, No. 2, April, 2011, pp. 181-186.

[0176] Specifically, the hollow aluminosilicate particles (A-1) produced in Production Example 1-1 were dried in a dry oven at 120°C for more than 3 hours, and then cooled to room temperature in a desiccator to remove adsorbed water before use. For the solvent, 300 ml was prepared by mixing ethanol and deionized water in a ratio of 80:20 (v / v%) at room temperature and atmospheric pressure, then the pH was adjusted to 3-5 using acetic acid, and the mixture was stirred at 300 rpm for about 30 minutes using a magnetic stirrer. 1 R is a methyl group, 2 ~R 425.0 g of compound (E-1), represented by chemical formula 1 and containing a methoxy group, was added and stirred at 300 rpm for 1 hour to hydrolyze the alkoxy group bonded to the Si end. After the hydrolysis reaction was complete, 5.0 g of the hollow aluminosilicate particles (A-1) from Production Example 1-1, from which the water had been removed, was placed in a round flask and subjected to a surface modification reaction at 300 rpm for 2 hours. The solution after the reaction was centrifuged at 3,000 rpm for 30 minutes using a centrifuge (SUPRA 21K, Hanil Science Co., Ltd.), and the supernatant was discarded. The solution was washed multiple times with ethanol / deionized water (80:20 v / v%) solution and pure ethanol, centrifuged, and then dried in a vacuum oven at 40°C for 24 hours to obtain surface-modified hollow aluminosilicate particles (F-1).

[0177] [Manufacturing Example 2-2: Manufacturing of surface-modified hollow aluminosilicate particles (F-2)] The aforementioned R 1 R is a methyl group, 2 ~R 4 Instead of the compound represented by chemical formula 1 (E-1), which has a methoxy group, R 1 is an ethyl group, R 2 ~R 4 Surface-modified hollow aluminosilicate particles (F-2) were produced in the same manner as in Production Example 2-1, except that a compound represented by chemical formula 1 (E-2), which is a methoxy group, was used.

[0178] [Manufacturing Example 2-3: Manufacturing of surface-modified hollow aluminosilicate particles (F-3)] The aforementioned R 1 R is a methyl group, 2 ~R 4 Instead of the compound represented by chemical formula 1 (E-1), which has a methoxy group, R 1 is a pentadecyl group, R 2 ~R 4 Surface-modified hollow aluminosilicate particles (F-3) were produced in the same manner as in Production Example 2-1, except that a compound represented by chemical formula 1 (E-3), which is an ethoxy group, was used.

[0179] [Production Example 2-4: Production of surface-modified hollow aluminosilicate particles (F-4)] The aforementioned R 1 is a methyl group, and instead of the compound represented by Chemical Formula 1 (E-1) in which R 2 to R 4 are methoxy groups, except that the compound represented by Chemical Formula 1 (E-4) in which R 1 is a pentacosanyl group and R 2 to R 4 are ethoxy groups was used, surface-modified hollow aluminosilicate particles (F-4) were produced by the same method as in Production Example 2-1.

[0180] [Production Example 2-5: Production of surface-modified hollow aluminosilicate particles (F-5)] The aforementioned R 1 is a methyl group, and instead of the compound represented by Chemical Formula 1 (E-1) in which R 2 to R 4 are methoxy groups, except that 3-aminopropyltriethoxysilane (KBM-903) (E-5) was used, surface-modified hollow aluminosilicate particles (F-5) were produced by the same method as in Production Example 2-1.

[0181] [Production Example 2-6: Production of surface-modified hollow aluminosilicate particles (F-6)] The aforementioned R 1 is a methyl group, and instead of the compound represented by Chemical Formula 1 (E-1) in which R 2 to R 4 are methoxy groups, except that 3-methacryloxypropyltrimethoxysilane (KBM-503) (E-6) was used, surface-modified hollow aluminosilicate particles (F-6) were produced by the same method as in Production Example 2-1.

[0182] [Production Example 2-7: Production of surface-modified hollow aluminosilicate particles (F-7)] The aforementioned R 1 is a methyl group, and R 2 to R 4Surface-modified hollow aluminosilicate particles (F-7) were produced by the same method as in Production Example 2-1 above, except that 3-mercaptopropylmethyldimethoxysilane (KBM-802) (E-7) was used in place of the compound (E-1) represented by Chemical Formula 1 in which R is a methoxy group.

[0183] [Production Example 2-8: Production of surface-modified hollow aluminosilicate particles (F-8)] Surface-modified hollow aluminosilicate particles (F-8) were produced by the same method as in Production Example 2-1 above, except that the hollow aluminosilicate particles (A-2) of Production Example 1-2 were used in place of the hollow aluminosilicate particles (A-1) of Production Example 1-1 above.

[0184] [Production Example 2-9: Production of surface-modified hollow aluminosilicate particles (F-9)] Surface-modified hollow aluminosilicate particles (F-9) were produced by the same method as in Production Example 2-1 above, except that the hollow aluminosilicate particles (A-3) of Production Example 1-3 were used in place of the hollow aluminosilicate particles (A-1) of Production Example 1-1 above.

[0185] [Production Example 2-10: Production of surface-modified hollow aluminosilicate particles (F-10)] The hollow aluminosilicate particles (A-4) of Production Example 1-4 were used in place of the hollow aluminosilicate particles (A-1) of Production Example 1-1 above, and the aforementioned R 1 is a methyl group, and R 2 to R 4 is a methoxy group; except for using the compound (E-2) represented by Chemical Formula 1, in which R 1 is an ethyl group, and R 2 to R 4 is a methoxy group, in place of the compound (E-1) represented by Chemical Formula 1 in which R1 to R3 are methoxy groups as described above, surface-modified hollow aluminosilicate particles (F-10) were produced by the same method as in Production Example 2-1 above.

[0186] [Manufacturing Example 2-11: Manufacturing of Surface-Modified Hollow Aluminosilicate Particles (F-11)] Instead of the hollow aluminosilicate particles (A-1) in Production Example 1-1, the hollow aluminosilicate particles (A-5) in Production Example 1-5 are used, and the R 1 R is a methyl group, 2 ~R 4 Instead of the compound represented by chemical formula 1 (E-1), which has a methoxy group, R 1 is an ethyl group, R 2 ~R 4 Surface-modified hollow aluminosilicate particles (F-11) were produced in the same manner as in Production Example 2-1, except that a compound represented by chemical formula 1 (E-2), which is a methoxy group, was used.

[0187] [Manufacturing Example 2-12: Manufacturing of Surface-Modified Hollow Aluminosilicate Particles (F-12)] The aforementioned R 1 R is a methyl group, 2 ~R 4 Surface-modified hollow aluminosilicate particles (F-12) were produced in the same manner as in Production Example 2-1, except that the non-reactive resin 1 (E-8) from Synthesis Example 1 was used instead of the compound (E-1) represented by chemical formula 1, which is a methoxy group.

[0188] [Manufacturing Example 2-13: Manufacturing of Surface-Modified Hollow Aluminosilicate Particles (F-13)] The aforementioned R 1 R is a methyl group, 2 ~R 4 In the same manner as in Production Example 2-1, surface-modified hollow aluminosilicate particles (F-13) were produced, except that the non-reactive resin 2 (E-9) from Synthesis Example 2 was used instead of the compound (E-1) represented by chemical formula 1, which is a methoxy group.

[0189] [Examples and Comparative Examples: Production of Resin Compositions for Anti-Reflection Coatings] Resin compositions for anti-reflective coatings were prepared by mixing the components according to the compositions shown in Tables 1 and 2 below (by weight %).

[0190] [Table 1]

[0191] [Table 2]

[0192] F-1~F-13: Surface-modified hollow aluminosilicate particles from manufacturing examples 2-1~2-13 B-1: PM-09 (average particle size 22nm, manufactured by Tokuyama Corporation) B-2:X-20 (average particle size 12nm, manufactured by Tokuyama Corporation) B-3: QSG-100 (average particle size 110 nm, manufactured by Shin-Etsu Chemical Co., Ltd.) C-1: Silicone resin (KR-220L, manufactured by Shin-Etsu Chemical Co., Ltd.) D-1: Propylene glycol monomethyl ether acetate E-1: BYK-110 (Phosphate-based dispersant, acid value 53 mg KOH / g) E-2: BYK-111 (Phosphate-based dispersant, acid value 129 mg KOH / g) E-3: DISPERBYK-192 (Carboxylic acid-based dispersant) E-4: DISPERBYK-108 (Carboxylic acid-based dispersant) E-5: DISPERBYK-2025 (acrylate-based dispersant).

[0193] [Experimental Example]: Anti-reflective coatings were manufactured using the resin compositions for anti-reflective coatings produced in the above examples and comparative examples, as described below, and the physical properties of the anti-reflective coatings were evaluated by the method described below. The results are shown in Tables 3 and 4 below.

[0194] Furthermore, the a / b values ​​were calculated and shown in Tables 3 and 4. Here, a is the average particle size of hollow aluminosilicate particles, and b is the average particle size of amorphous silica particles.

[0195] <Manufacturing of anti-reflective coatings> The anti-reflective resin compositions produced in the above examples and comparative examples were spin-coated onto 4-inch silicon wafers (manufactured by SK Siltron), and then pre-baked at 100°C for 60 seconds using a hot plate. After the pre-baked substrates were cooled to room temperature, they were post-baked in a 200°C oven for 300 seconds. The thickness of the cured film was 100 nm.

[0196] (1) Refractive index measurement Linear polarization was measured in the wavelength range of 200 nm to 1000 nm using an ellipsometer M-2000 (manufactured by JA Woollam Co.) at incident angles of 65, 70, and 75° under conditions of 25°C and 50% RH. The measured linear polarization measurement data (Ellipsometry data (Ψ, Δ)) was optimized (fitted) using CompleteEASE software to the Cauchy model (Equation 2 below) so that the MSE was 20 or less, and the refractive index at a wavelength of 550 nm was calculated. The refractive index was evaluated according to the evaluation criteria below.

[0197]

number

[0198] In the above mathematical formula 2, n(λ) is the refractive index at wavelength λ, λ is in the range of 300 nm to 1800 nm, and A, B, and C are Cauchy parameters.

[0199] <Evaluation Criteria> ◎: Refractive index 1.10 or higher and less than 1.25 ○: Refractive index 1.25 or higher and 1.35 or lower ×: Refractive index greater than 1.35.

[0200] (2) Crack resistance A cured film substrate was manufactured in the same manner as described above, except that the cured film thickness was 500 nm.

[0201] The surface of the cured film substrate was visually observed to check whether cracks occurred, and crack resistance was evaluated according to the following evaluation criteria.

[0202] <Evaluation Criteria> ○: No cracks occurred ×: Cracks occurred.

[0203] (3) Flatness of coating film The Ra value of the produced cured film substrate was measured with an atomic force microscope (AFM) Nanoscope (manufactured by Bruker AXS), and the flatness of the coating film was evaluated according to the following evaluation criteria.

[0204] <Evaluation Criteria> ◎: Ra value is less than 6 nm ○: Ra value is 6 nm or more and less than 9 nm ×: Ra value is 9 nm or more.

[0205] (4) Moisture vapor transmission rate under high temperature and high humidity The produced cured film substrate was stored in a constant temperature and humidity chamber PR-1J (manufactured by ESPEC) at a temperature of 85°C and a humidity of 85% for 500 hours, and the refractive index before and after storage was measured. The change in refractive index was calculated by the following Mathematical Formula 3. The moisture vapor transmission rate under high temperature and high humidity was evaluated according to the following evaluation criteria. [Mathematical Formula 3] Change in refractive index = [(Refractive index after storage - Refractive index before storage) / Refractive index before storage] × 100 <Evaluation Criteria> ◎: Less than 1% ○: 1% or more and less than 5% ×: 5% or more.

[0206] (5) Vapor transmission rate with respect to developer and stripping solution For the produced cured film substrate, the refractive index before and after 5 minutes of immersion in 2.38% tetramethylammonium hydroxide (TMAH) (developer) and methylpyrrolidone (stripping solution) respectively was measured, and the change in refractive index was calculated by the following Mathematical Formula 4. The vapor transmission rate with respect to developer and stripping solution was evaluated according to the following evaluation criteria. [Mathematical formula 4] Change in refractive index = [(refractive index after immersion - refractive index before immersion) / refractive index before immersion]×100 <Evaluation Criteria> ⊙: Less than 1% ○: 1% or more and less than 5% ×: 5% or more.

[0207] (6) Foreign Matter Level Contamination measurement was performed on the produced cured film substrate using KEYENCE (VHX-S770E). The number of foreign matters was counted, and the foreign matter level was evaluated according to the following evaluation criteria.

[0208] <Evaluation Criteria> ⊙: Less than 50 particles ○: 50 particles or more and less than 100 particles ×: 100 particles or more.

[0209] (7) Particle Size Change Stability For the resin compositions for antireflection films produced in the above Examples and Comparative Examples, the initial average particle size and the average particle size after storage at normal temperature (23°C) for 30 days were measured respectively using ELSZ-2000ZS (manufactured by Otsuka Electronics Co., Ltd.). The particle size change stability was evaluated from the calculated particle size change rate according to the following evaluation criteria.

[0210] <Evaluation Criteria> ○: Particle size change rate less than 5% △: Particle size change rate 5% or more and less than 10% ×: Particle size change rate 10% or more.

[0211] (8) Sedimentation Stability The sedimentation stability of the resin compositions for antireflection films produced in the above Examples and Comparative Examples was evaluated using a TURBISCAN LAB instrument. 30 ml of the resin composition for antireflection film was placed into a 40 ml vial for Turbiscan measurement, and the Turbiscan Stability Index (TSI) after standing at normal temperature (23°C) for 30 days was confirmed.

[0212] Based on TSI, seismic stability was evaluated from A+ to D according to the following evaluation criteria.

[0213] <Evaluation Criteria> A+: A stable state with almost no change in the sample. A: There are some slight changes in stability, but overall, the stability is good. B: Although not visible to the naked eye, there is a change in the stability of the sample to some extent. C: A state where changes become visible to the naked eye. D: A state in which phase separation is clearly evident.

[0214] [Table 3]

[0215] [Table 4]

[0216] As shown in Tables 3 and 4 above, the resin compositions for anti-reflective coatings of Examples 1 to 12, which contain hollow aluminosilicate particles with a Si / Al molar ratio of 7 to 15 and whose surface is modified with a compound represented by chemical formula 1 or a non-reactive resin, and a phosphate-based dispersant as an additive, exhibit a low refractive index, suppress the occurrence of cracks during coating film formation, have excellent coating film flatness, prevent particle aggregation and foreign matter generation, prevent moisture adsorption under high temperature and high humidity conditions, prevent moisture permeation by developing and stripping solutions, and also exhibit excellent particle size change stability and sedimentation stability.

[0217] On the other hand, the resin compositions for anti-reflective coatings of Comparative Examples 1 to 12 showed results such as an increase in refractive index, poor crack resistance and / or flatness of the coating film, generation of foreign matter, moisture permeation under high temperature and high humidity conditions, moisture permeation by developing and stripping solutions, or decreased particle size change stability and / or sedimentation stability.

[0218] Although specific parts of the present invention have been described in detail above, it is clear to any person with ordinary skill in the art to which the present invention belongs that such specific technologies are merely preferred embodiments and do not limit the scope of the present invention. A person with ordinary skill in the art to which the present invention belongs will be able to make various applications and modifications within the scope of the present invention based on the above content.

[0219] Therefore, the substantial scope of the present invention can be defined by the claims and their equivalents.

Claims

1. It comprises hollow aluminosilicate particles, a binder resin, a solvent, and additives. The hollow aluminosilicate particles have a Si / Al molar ratio of 7 to 15, and their surface is modified with a compound represented by the following chemical formula 1 or a non-reactive resin. The aforementioned additive is a resin composition for anti-reflective coatings, comprising a phosphate-based dispersant. 【Chemistry 1】 In the above formula, R １ C １ -C ２０ It is an alkyl group, R ２ ~R ４ Each of them is independently C １ -C ４ It is an alkoxy group.

2. The resin composition for anti-reflective coatings according to claim 1, wherein the average particle size of the hollow aluminosilicate particles is 30 to 150 nm.

3. The resin composition for anti-reflective coatings according to claim 1, wherein the non-reactive resin comprises repeating units represented by the following chemical formula 2. 【Chemistry 2】 In the above formula, R ５ is a hydrogen atom or a methyl group, L １ is absent, or C １ -C １０ alkylene group or C １ -C １０ oxyalkylene group, R ６ C is a hydroxyl group. １ -C ４ It is an alkoxy group or halogen, R ７ is a hydrogen atom or C １ -C ２０ It is an alkyl group, n is an integer between 1 and 3.

4. The resin composition for anti-reflective coatings according to claim 1, wherein the phosphate-based dispersant has an acid value of 20 to 150 mg KOH / g.

5. The resin composition for anti-reflective coatings according to claim 1, wherein the phosphate-based dispersant is contained in an amount of 0.01 to 10% by weight based on 100% by weight of the total solids content in the resin composition for anti-reflective coatings.

6. The resin composition for anti-reflective coatings according to claim 1, further comprising amorphous silica particles.

7. A resin composition for an anti-reflective coating according to claim 6, satisfying the following mathematical formula 1. [Mathematical formula 1] 1 ≤ a / b ≤ 15 In the above formula, a is the average particle size of hollow aluminosilicate particles, and b is the average particle size of amorphous silica particles.

8. The resin composition for anti-reflective coatings according to claim 1, wherein the cured film formed from the resin composition for anti-reflective coatings has a refractive index of 1.10 to 1.35 at 550 nm.

9. An anti-reflective film formed using the resin composition for anti-reflective films described in any one of claims 1 to 8.

10. A solid-state image sensor comprising the anti-reflective coating described in claim 9.

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