Resin composition for Anti-reflective film, Anti-reflective film, and solid-state imaging device

Abstract

The present invention provides a resin composition for an anti-reflective film, an anti-reflective film formed therefrom, and a solid-state imaging device comprising the anti-reflective film, the resin composition comprising hollow aluminosilicate particles, amorphous silica particles, a first binder resin having a curable functional group and a hydrolyzable silyl group, a thermal polymerization initiator and a solvent, wherein the hollow aluminosilicate particles have an Si / Al molar ratio of 7 to 15, and the surface thereof is modified with a second binder resin having a curable functional group and a hydrolyzable silyl group. If a coating film is formed using the resin composition for an anti-reflective film, according to the present invention, crack formation is suppressed, the coating film has excellent flatness, moisture absorption under high temperature and high humidity is prevented, and permeability due to developer and stripping solution can be prevented.

Description

Resin composition for antireflection film, antireflection film and solid-state imaging device

[0001] The present invention relates to a resin composition for an anti-reflection film, an anti-reflection film, and a solid-state imaging device, and more specifically, to a resin composition for an anti-reflection film, an anti-reflection film, and a solid-state imaging device, which suppresses the occurrence of cracks during film formation, has excellent film flatness, prevents moisture adsorption under high temperature and high humidity, and can prevent moisture penetration by a developer and a stripper.

[0002] A solid-state image sensor is a device that converts images captured via optical energy into electrical information. Microlenses for light collection are formed on the photoelectric conversion element, and an anti-reflection film is formed on its surface. This anti-reflection film prevents noise such as flare and ghosting.

[0003] Antireflection coatings applied to solid-state imaging devices require precise and precise processing and formability. For this reason, vapor deposition methods, such as vacuum deposition and sputtering, which are suitable for conventional microfabrication, have been employed.

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

[0005] Accordingly, a coating method is proposed in which a composition capable of forming an anti-reflection film is applied to a substrate and cured to replace the vapor deposition method.

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

[0007] However, the conventional antireflection film composition using hollow silica particles has problems in that cracks are likely to occur during film formation, the flatness of the film is poor, moisture adsorption occurs under high temperature and high humidity, and moisture penetration occurs by a developer and a stripper.

[0008] Therefore, there is a need for the development of a resin composition for an anti-reflection film that suppresses cracking during film formation, has excellent film flatness, prevents moisture absorption under high temperature and high humidity, and prevents moisture penetration by a developer and a stripper.

[0009] One object of the present invention is to provide a resin composition for an antireflection film that suppresses the occurrence of cracks during film formation, has excellent film flatness, prevents moisture absorption under high temperature and high humidity, and can prevent moisture penetration by a developer and a stripper.

[0010] Another object of the present invention is to provide an antireflection film formed using the above-described resin composition for an antireflection film.

[0011] Another object of the present invention is to provide a solid-state imaging device having the above-described anti-reflection film.

[0012] On the one hand, the present invention comprises hollow aluminosilicate particles, amorphous silica particles, a first binder resin having a curable functional group and a hydrolyzable silyl group, a thermal polymerization initiator, and a solvent,

[0013] The hollow aluminosilicate particles have a Si / Al molar ratio of 7 to 15, and the surface thereof is modified with a second binder resin having a curable functional group and a hydrolyzable silyl group, thereby providing a resin composition for an antireflection film.

[0014]

[0015] A resin composition for an anti-reflection film according to one embodiment of the present invention can satisfy the following mathematical expression 1.

[0016] [Mathematical Formula 1]

[0017] 3 ≤ a / b ≤ 15

[0018] In the above formula,

[0019] a is the average particle diameter of hollow aluminosilicate particles, and b is the average particle diameter of amorphous silica particles.

[0020]

[0021] In one embodiment of the present invention, the average particle diameter of the hollow aluminosilicate particles may be 30 to 150 nm.

[0022] In one embodiment of the present invention, the first binder resin and the second binder resin may each independently include a repeating unit represented by the following chemical formula 1 and a repeating unit represented by the following chemical formula 2.

[0023] [Chemical Formula 1]

[0024]

[0025] [Chemical Formula 2]

[0026]

[0027] In the above formula,

[0028] R 1 , R 3 and R 4 are each independently a hydrogen atom or a methyl group,

[0029] R 2 is a residue containing a carboxylic acid derived by a hydrogen atom or an acid anhydride,

[0030] L 1 does not exist or C1-C 10 alkylene group or C1-C 10 is an oxyalkylene group,

[0031] R 5 is a hydroxy group, a C1-C4 alkoxy group or halogen,

[0032] R 6 is a hydrogen atom or C1-C 20 is an alkyl group,

[0033] n is an integer from 1 to 3.

[0034]

[0035] In one embodiment of the present invention, the first binder resin and the second binder resin may each independently further include a repeating unit represented by the following chemical formula 3.

[0036] [Chemical Formula 3]

[0037]

[0038] In the above formula,

[0039] R 7 is a hydrogen atom or a methyl group,

[0040] L 2 does not exist or C1-C 18 is an alkylene group.

[0041]

[0042] In one embodiment of the present invention, the molar ratio of the repeating unit represented by the chemical formula 1 and the repeating unit represented by the chemical formula 2 may be 10:90 to 90:10.

[0043] In one embodiment of the present invention, the repeating unit represented by the above chemical formula 3 may be included in an amount of 1 to 30 mol% based on 100 mol% of the total repeating units constituting the binder resin.

[0044]

[0045] The resin composition for an anti-reflection film according to one embodiment of the present invention may further include a leveling agent.

[0046] In one embodiment of the present invention, a cured film formed from the resin composition for the anti-reflection film may have a refractive index of 1.20 to 1.35 at 550 nm.

[0047]

[0048] On the other hand, the present invention provides an antireflection film formed using the resin composition for the antireflection film.

[0049] On the other hand, the present invention provides a solid-state imaging device having the above-described anti-reflection film.

[0050] The resin composition for an anti-reflection film according to the present invention suppresses the occurrence of cracks during film formation, provides excellent film flatness, prevents moisture absorption under high temperature and high humidity, and can block moisture penetration by a developer and a stripper. Therefore, the resin composition for an anti-reflection film according to the present invention can be advantageously applied to an anti-reflection film for a solid-state imaging device.

[0051] Hereinafter, the present invention will be described in more detail.

[0052]

[0053] One embodiment of the present invention comprises hollow aluminosilicate particles (A), amorphous silica particles (B), a first binder resin (C) having a curable functional group and a hydrolyzable silyl group, a thermal polymerization initiator (D), and a solvent (E).

[0054] The hollow aluminosilicate particles (A) described above have a Si / Al molar ratio of 7 to 15 and are surface-modified with a second binder resin having a curable functional group and a hydrolyzable silyl group, and relate to a resin composition for an antireflection film.

[0055]

[0056] The above Si / Al molar ratio refers to the molar ratio of the silicon (Si) element in the hollow aluminosilicate particles and the aluminum (Al) element used for modification.

[0057] The Si / Al molar ratio is 7 to 15 as described above, preferably 7 to 12. If the Si / Al molar ratio is less than 7, the aluminum content increases, and a completely hollow shape may not be formed due to micropores generated on the surface of the shell, which reduces the strength of the hollow particles and makes it impossible to manufacture high-density hollow particles. In addition, aluminum that is not dissolved in the shell may exist, which may increase the refractive index. If it is greater than 15, when forming micropores in the shell, not only aluminum on the surface of the shell but also core particles may not be completely removed, which may increase the refractive index, and it may be difficult to maintain the shape of the hollow shape in a hydrothermal reaction.

[0058]

[0059] A resin composition for an anti-reflection film according to one embodiment of the present invention can satisfy the following mathematical expression 1.

[0060] [Mathematical Formula 1]

[0061] 3 ≤ a / b ≤ 15

[0062] In the above formula,

[0063] a is the average particle diameter of hollow aluminosilicate particles, and b is the average particle diameter of amorphous silica particles.

[0064]

[0065] The above a / b value is the average particle size ratio of hollow aluminosilicate particles to amorphous silica particles. If the above a / b value is less than 3, the refractive index increases due to the amorphous silica particles having large particle sizes, and the amorphous silica particles may not sufficiently fill the spaces between the hollow aluminosilicate particles, which may reduce the flatness of the coating film. If the a / b value is greater than 15, the flatness of the coating film may reduce due to the hollow aluminosilicate particles having large particle sizes.

[0066]

[0067] In one embodiment of the present invention, a cured film formed from the resin composition for the anti-reflection film may have a refractive index of 1.20 to 1.35 at 550 nm.

[0068] By controlling the refractive index at 550 nm of the cured film formed from the above-mentioned anti-reflection film resin composition within the above range, the light collection efficiency of the solid-state imaging device can be improved by eliminating noise such as flare or ghost by positioning it on top of a high-refractive-index layer having a refractive index of 1.60 or higher.

[0069]

[0070] Hollow aluminosilicate particles (A)

[0071] In one embodiment of the present invention, the hollow aluminosilicate particles (A) serve to improve antireflection properties by lowering the refractive index while maintaining the strength of the coating film.

[0072] The above hollow aluminosilicate particles (A) are silica particles modified with Al, and the Si / Al molar ratio is 7 to 15, preferably 7 to 12.

[0073] As the above hollow aluminosilicate particles (A) are modified with Al, they have low cohesion and excellent dispersibility, and can have a high density through a hydrothermal reaction.

[0074] The hollow aluminosilicate particles can be obtained by forming a core-shell particle in which an aluminosilicate shell is formed by reacting a silane compound and an aluminum (Al) precursor with a template core formed of micelles or reverse micelles of an organic polymer, and then reacting the core-shell particle with a basic aqueous solution or an acidic aqueous solution to form micropores in the shell, and simultaneously removing the core. If necessary, the hollow aluminosilicate particles can be further subjected to a hydrothermal reaction to increase their density.

[0075] The organic polymer forming the above micelle or reverse micelle is an amphoteric polymer having hydrophobicity and hydrophilicity, and may be, for example, polyoxyethylene tallowamine, polyoxyethylene olylamine, polyoxyethylene sterylamine, polyoxyethylene laurylamine, polyoxyethylene sorbitan ester, polyoxyethylene octyl ether, etc. These organic polymers may be used alone or in combination of two or more.

[0076] The above organic polymer forms micelles or reverse micelles in a solvent. At this time, the type of solvent is not particularly limited and can be selected and used depending on the characteristics of the organic polymer. Specifically, the solvent can be an alcohol, a glycol ester, a ketone, or a mixed solvent thereof. The alcohol can be methanol, ethanol, isopropanol, etc., the glycol ester can be methyl cellosolve, ethyl cellosolve, etc., and the ketone can be methyl ethyl ketone, methyl isobutyl ketone, etc.

[0077] The above silane compound can be easily combined with an organic polymer forming a template core. This combination can be performed by the Stober method (Werner, 1968), and when manufacturing a shell using a sol-gel process using the Stober method, a stable shell can be manufactured through hydrolysis and condensation polymerization using an acidic solution or basic solution contained in the solvent.

[0078] As the above silane compound, alkoxysilane, chlorosilane, bromosilane, alkylsilane, etc. can be used without limitation. For example, as the above silane compound, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylchlorosilane, trimethylbromosilane, etc. can be used. These silane compounds can be used alone or in combination of two or more.

[0079] The type of the above aluminum precursor is not particularly limited, and for example, an organic salt or alkoxide of aluminum can be used.

[0080] The above silane compound and aluminum precursor combine with the core material to form an aluminosilicate shell, thereby producing core-shell particles. The core-shell particles thus produced can be reacted with a basic aqueous solution or an acidic aqueous solution to form micropores in the shell, and the micropores thus formed facilitate the entry and exit of dissolved organic polymers, so that the organic polymers inside the shell can be easily removed through a simple washing step.

[0081] As the above basic aqueous solution, sodium hydroxide, ammonium hydroxide, potassium hydroxide, phosphate hydroxide or a mixed aqueous solution thereof can be used, and as the above acidic aqueous solution, hydrochloric acid, nitric acid, sulfuric acid, acetic acid or a mixed aqueous solution thereof can be used.

[0082] The above-mentioned washing solvent may be distilled water, alcohol, glycol, glycol ester, or a mixed solvent thereof. The alcohol may be methanol, ethanol, isopropanol, etc., the glycol may be ethylene glycol, propylene glycol, etc., and the glycol ester may be ethyl cellosolve, methyl cellosolve, etc.

[0083] The above-mentioned hydrothermal reaction can be carried out at a temperature of 160 to 250°C.

[0084]

[0085] In one embodiment of the present invention, the average particle diameter of the hollow aluminosilicate particles may be 30 to 150 nm, preferably 60 to 120 nm, and more preferably 80 to 100 nm. When the average particle diameter of the hollow aluminosilicate particles is within the above range, it is easy to control so as to satisfy the above mathematical expression 1, and the refractive index of the cured film can be more effectively controlled. When the average particle diameter of the hollow aluminosilicate particles is less than 30 nm, the volume of air within the hollow aluminosilicate particles decreases, making it difficult to lower the refractive index, and the hollow shape may be difficult to maintain due to the thin shell thickness, easily breaking. When it exceeds 150 nm, the flatness of the coating film deteriorates, and a difference in refractive index may occur within the coating film.

[0086]

[0087] The above hollow aluminosilicate particles are surface-modified with a second binder resin having a curable functional group and a hydrolyzable silyl group.

[0088] In one embodiment of the present invention, the second binder resin may be selected and used without any particular limitation from any resin known in the art, as long as it has a curable functional group that is reactive by the action of light or heat and a hydrolyzable silyl group that can be bonded to the surface of hollow aluminosilicate particles.

[0089] Preferably, as the second binder resin, a binder resin including a repeating unit represented by the following chemical formula 1 and a repeating unit represented by the following chemical formula 2 can be used in terms of high temperature and high humidity resistance of the formed coating film and resistance to a developer and a stripping agent.

[0090] [Chemical Formula 1]

[0091]

[0092] [Chemical Formula 2]

[0093]

[0094] In the above formula,

[0095] R 1 , R 3 and R 4 are each independently a hydrogen atom or a methyl group,

[0096] R 2 is a residue containing a carboxylic acid derived by a hydrogen atom or an acid anhydride,

[0097] L 1 does not exist or C1-C 10 alkylene group or C1-C 10 is an oxyalkylene group,

[0098] R 5 is a hydroxy group, a C1-C4 alkoxy group or halogen,

[0099] R 6 is a hydrogen atom or C1-C 20 is an alkyl group,

[0100] n is an integer from 1 to 3.

[0101]

[0102] The acid anhydride used in this specification is 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, trimellitic anhydride, Examples thereof include, but are not limited to, hexahydrophthalic anhydride, carbic anhydride, etc. In terms 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 more preferable.

[0103] C1-C as used in this specification 10 The alkylene group refers to a straight-chain or branched divalent hydrocarbon having 1 to 10 carbon atoms, and examples thereof include, but are not limited to, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, etc.

[0104] C1-C as used in this specification 10The oxyalkylene group refers to a functional group in which at least one of the chain carbons is replaced with oxygen in a straight-chain or branched divalent hydrocarbon having 1 to 10 carbon atoms, and examples thereof include, but are not limited to, oxymethylene, oxyethylene, oxypropylene, oxybutylene, oxypentylene, and oxyhexylene.

[0105] The C1-C4 alkoxy group used in this specification means a straight-chain or branched alkoxy group consisting of 1 to 4 carbon atoms, and includes, but is not limited to, methoxy, ethoxy, n-propanoxy, etc.

[0106] C1-C as used in this specification 20 The alkyl group of refers to a straight-chain or branched monovalent hydrocarbon having 1 to 20 carbon atoms, and examples thereof include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, n-decyl, and the like.

[0107]

[0108] The second binder resin may further include a repeating unit represented by the following chemical formula 3 in order to improve the degree of curing of the coating film, thereby improving the high temperature and high humidity resistance of the formed coating film and the resistance to a developer and a stripper.

[0109] [Chemical Formula 3]

[0110]

[0111] In the above formula,

[0112] R 7 is a hydrogen atom or a methyl group,

[0113] L2 does not exist or C1-C 18 is an alkylene group.

[0114]

[0115] C1-C as used in this specification 18 The alkylene group refers to a straight-chain or branched divalent hydrocarbon having 1 to 18 carbon atoms, and examples thereof include, but are not limited to, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, etc.

[0116]

[0117] Preferably, L 2 may not exist or may be an alkylene group of C1-C6.

[0118]

[0119] In one embodiment of the present invention, the molar ratio of the repeating unit represented by the chemical formula 1 and the repeating unit represented by the chemical formula 2 may be 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and even more preferably 40:60 to 60:40. When the molar ratio of the repeating unit represented by the chemical formula 1 and the repeating unit represented by the chemical formula 2 is within the above range, the formed coating film has excellent high temperature and high humidity resistance and resistance to a developer and a stripper.

[0120] In one embodiment of the present invention, the repeating unit represented by the above chemical formula 1 and the repeating unit represented by the chemical formula 2 may be included in an amount of 70 to 99 mol%, preferably 80 to 97 mol%, and more preferably 90 to 95 mol%, based on 100 mol% of the total repeating units constituting the binder resin. When the repeating unit represented by the above chemical formula 1 and the repeating unit represented by the chemical formula 2 are included within the above mol% range, the formed coating film has excellent high temperature and high humidity resistance and resistance to a developer and a stripper.

[0121] In one embodiment of the present invention, the repeating unit represented by the above chemical formula 3 may be included in an amount of 1 to 30 mol%, preferably 3 to 20 mol%, and more preferably 5 to 10 mol%, based on 100 mol% of the total repeating units constituting the binder resin. When the repeating unit represented by the above chemical formula 3 is included within the above mol% range, curing in the form of a three-dimensional network within the coating film can be easily achieved, thereby improving the hardness of the coating film.

[0122]

[0123] The above second binder resin may be a block copolymer in which the repeating units represented by the chemical formulae 1 to 3 are each regularly repeated, or a random copolymer in which these are randomly repeated.

[0124] In the present invention, the repeating unit or compound represented by the chemical formula includes isomers of the repeating unit or compound, and if there are isomers of the repeating unit or compound represented by each chemical formula, the repeating unit or compound represented by the chemical formula includes even the isomers.

[0125]

[0126] The method for manufacturing the above second binder resin is not particularly limited, and a method known in the art can be used.

[0127] For example, the second binder resin can be manufactured by copolymerizing a monomer represented by the following chemical formula 1a and a monomer represented by the following chemical formula 2a.

[0128] [Chemical Formula 1a]

[0129]

[0130] [Chemical Formula 2a]

[0131]

[0132] In the above formula,

[0133] R 1 , R 3and R 4 are each independently a hydrogen atom or a methyl group,

[0134] R 2 is a residue containing a carboxylic acid derived by a hydrogen atom or an acid anhydride,

[0135] L 1 does not exist or C1-C 10 alkylene group or C1-C 10 is an oxyalkylene group,

[0136] R 5 is a hydroxy group, a C1-C4 alkoxy group or halogen,

[0137] R 6 is a hydrogen atom or C1-C 20 is an alkyl group,

[0138] n is an integer from 1 to 3.

[0139]

[0140] If necessary, a monomer represented by the following chemical formula 3a may be further used as a monomer during the copolymerization.

[0141] [Chemical Formula 3a]

[0142]

[0143] In the above formula,

[0144] R 7 is a hydrogen atom or a methyl group,

[0145] L 2 does not exist or C1-C 18 is an alkylene group.

[0146]

[0147] Alternatively, R 2 is a hydrogen atom and L 2If the second binder resin does not exist, the second binder resin can be prepared by copolymerizing the monomer represented by the above chemical formula 3a and the monomer represented by the above chemical formula 2a, and then reacting the prepared copolymer with glycidyl (meth)acrylate. At this time, the amount of each monomer used can be controlled so as to satisfy the molar ratio and molar % of each repeating unit described above.

[0148]

[0149] Also, R 2 A residue containing a carboxylic acid derived from an acid anhydride and L 2 If the second binder resin does not exist, the second binder resin can be prepared by copolymerizing glycidyl (meth)acrylate with a monomer represented by the above chemical formula 2a, reacting the prepared copolymer with a monomer represented by the above chemical formula 3a, and then reacting the copolymer that has undergone the reaction with an acid anhydride. At this time, the amount of each monomer used can be controlled so as to satisfy the molar ratio and mol% of each repeating unit described above.

[0150]

[0151] The method for producing the above copolymer is not particularly limited, and any conventionally known polymerization method may be used. Among the known polymerization methods, solution polymerization is preferred. Furthermore, the polymerization temperature and time vary depending on the type and ratio of the introduced monomers and the molecular weight of the desired resin, but, for example, polymerization can be performed at 60 to 130°C for 1 to 10 hours.

[0152] When using a solvent during the above polymerization, a solvent used in a typical radical polymerization reaction can be used, and specifically, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide, etc. can be used. These solvents can be used alone or in combination of two or more.

[0153] As a polymerization initiator used in the above polymerization, a commonly used polymerization initiator can be added and is not particularly limited. Specifically, organic peroxides such as diisopropylbenzene hydroperoxide, di-t-butylperoxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, and t-butylperoxy-2-ethylhexanoate; nitrogen compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl 2,2'-azobis(2-methylpropionate) can be mentioned. These can be used alone or in combination of two or more.

[0154] During the above polymerization, a chain transfer agent may be used to control the molecular weight or molecular weight distribution of the copolymer. Examples of the chain transfer agent include mercapto compounds such as n-dodecanethiol, mercaptoacetic acid, and methyl mercaptoacetate; α-methylstyrene dimer, and the like.

[0155]

[0156] The second binder resin may have a polystyrene-converted weight average molecular weight (hereinafter simply referred to as “weight average molecular weight”) of 1,000 to 30,000, as measured by gel permeation chromatography (GPC; using tetrahydrofuran as an eluting solvent). When the weight average molecular weight of the second binder resin is within the above range, the hardness of the coating film may be improved, and the reliability of solvent resistance and the like may be improved.

[0157]

[0158] Surface modification of the hollow aluminosilicate particles can be performed by hydrolyzing the hydrolyzable silyl group of the second binder resin to form a silanol (-Si-OH) group, which is then reacted with the hollow aluminosilicate particles.

[0159]

[0160] The hollow aluminosilicate particles may be included in an amount of 20 to 70 wt%, preferably 40 to 60 wt%, based on 100 wt% of the total solid content of the resin composition for an anti-reflection film. If the hollow aluminosilicate particles are included in an amount less than 20 wt%, the low-refractive effect cannot be exhibited, and thus the function of the anti-reflection film cannot be exerted. If the hollow aluminosilicate particles are included in an amount exceeding 70 wt%, it is not easy to form a coating film, and due to the relatively reduced content of amorphous silica particles, the spaces between large-diameter hollow aluminosilicate particles cannot be filled with small-diameter amorphous silica particles, and thus the flatness of the coating film may be reduced.

[0161]

[0162] Amorphous silica particles (B)

[0163] In one embodiment of the present invention, the amorphous silica particles (B) serve to suppress crack occurrence and improve the flatness of the coating film while maintaining the coating film strength.

[0164] The above amorphous silica particles (B) are silica particles that do not have a hollow space inside their structure and have no regularity in particle shape.

[0165] The above amorphous silica particles (B) can be obtained and used commercially.

[0166] 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, X-30 (manufactured by Tokuyama Co., Ltd.).

[0167] In one embodiment of the present invention, the average particle diameter of the amorphous silica particles may be 7 to 25 nm, preferably 7 to 22 nm. If the average particle diameter of the amorphous silica particles is within the above range, it may be easy to control so as to satisfy the above mathematical expression 1, and the refractive index of the cured film may be more effectively controlled. If the average particle diameter of the amorphous silica particles is less than 7 nm, gelation of the particles during storage may not be suppressed, and if it exceeds 25 nm, the surface roughness of the coating film may increase and haze may occur.

[0168]

[0169] The amorphous silica particles may be included in an amount of 20 to 70 wt%, preferably 30 to 50 wt%, based on 100 wt% of the total solid content of the resin composition for an antireflection film. If the amorphous silica particles are included in an amount less than 20 wt%, the filling between the hollow aluminosilicate particles in the coating film may not be sufficiently achieved, thereby increasing the surface roughness of the coating film. If the amorphous silica particles are included in an amount exceeding 70 wt%, the content of the hollow aluminosilicate particles may be relatively reduced, making it difficult to lower the refractive index.

[0170]

[0171] First binder resin (C)

[0172] In one embodiment of the present invention, the first binding agent resin (C) has reactivity due to the action of light or heat, and any resin known in the art can be selected and used without any particular limitation as long as it performs the function of a binding resin.

[0173] The above first binder resin may have a curable functional group and a hydrolyzable silyl group, and preferably, the above-described second binder resin may be used.

[0174] The first binder resin and the second binder resin may be the same or different.

[0175]

[0176] The first binder resin may be included in an amount of 3 to 20 wt%, preferably 4 to 15 wt%, based on 100 wt% of the total solid content of the resin composition for an anti-reflection film. If the first binder resin is included in an amount of less than 3 wt%, curing in a three-dimensional network shape does not occur, so that moisture permeation can be easily achieved in a high temperature and high humidity environment, a stripper, and a developer, and the refractive index can increase. If the first binder resin is included in an amount of more than 20 wt%, the content of hollow aluminosilicate particles and amorphous silica particles is relatively reduced, so that the refractive index can increase.

[0177]

[0178] Thermal polymerization initiator (D)

[0179] In one embodiment of the present invention, the thermal polymerization initiator (D) may be a thermal radical polymerization initiator that generates radicals by the action of heat.

[0180] The above thermal polymerization initiator is not particularly limited, but may include azo compounds, organic peroxides, etc.

[0181] Examples of the above azo compounds include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methyl) dihydrochloride, 1,1'-azobis(1-acetoxy-1-phenylethane, 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis(isobutyrate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), Examples include 1-[(1-cyano-1-methylethyl)azo]formamide, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, and dimethyl-2,2'-azobis(2-methylpropionate).

[0182] Examples of the organic peroxides include benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, methyl ethyl ketone peroxide, 1,1-di(t-hexylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, n-butyl 4,4-di-(t-butylperoxy)valerate, 2,2-di(4,4-di-(t-butylperoxy)cyclohexyl)propane, p-menthane hydroperoxide, diisopropoxylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, di-(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3, diisobutyryl peroxide, di(3,5,5-t-methylhexanoyl)peroxide, dilauroyl peroxide, disuccinic peroxide, di-(3-methylbenzoyl)peroxide, dibenzoyl peroxide, di-n-propylperoxycarbonate, di-isopropylperoxydicarbonate, di(4-t-butylcyclohexyl)peroxycarbonate, di(2-ethylhexyl)peroxycarbonate, di-sec-butylperoxycarbonate, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, t-Hexylperoxyneodecanoate, t-Butylperoxyneodecanoate, t-Hexylperoxypivalate, t-Butylperoxypivalate, 1,1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(t-ethylhexanoylperoxy)hexane, t-Hexylperoxy-2-ethylhexanoate, t-Butylperoxy-2-ethylhexanoate, t-Hexylperoxyisopropylmonocarbonate, t-Butylperoxy-3,5,5-trimethylhexanoate, t-Butylperoxylaurate, t-Butylperoxyisopropylmonocarbonate, t-Butylperoxy-2-ethylhexylmonocarbonate, t-Hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, a mixture of t-butylperoxy-3-methylbenzoate and t-butylperoxybenzoate, t-butylperoxybenzoate, t-butylperoxyallyl monocarbonate,Examples include 3,3',4,4'-tetra(t-butylperoxycarbol)benzophenone, etc.

[0183] Commercially available products of the above thermal polymerization initiator include azo nitrile-based products V-60, V-65, V-59, V-70, V-40, azo ester-based products V-601, azo amide-based products VA-086, VA-085, VA-080, Vam-110, Vam-111, VF-096, azo amidine-based products V-50, VA-044, VA-046B, Aam-027, VA-060, VA-057, VA-061, and macroazo-based initiators VPS-0501, VPS-1001, VPE-0201, VPE-0401, VPE-0601, VPTG-0301, etc., all from Wako Pure Chemical Industris. Ltd.

[0184] The above thermal polymerization initiator may be included in an amount of 0.01 to 10 wt%, preferably 0.03 to 7 wt%, based on 100 wt% of the total solid content of the resin composition for an antireflection film. If the content of the thermal polymerization initiator is less than the above range, curing in a three-dimensional network shape does not occur, so that moisture permeation may easily occur in a high-temperature, high-humidity environment, a stripping agent, and a developing agent. If the content exceeds the above range, the content of hollow aluminosilicate particles and amorphous silica particles may relatively decrease, so that the refractive index may increase.

[0185]

[0186] Solvent (E)

[0187] The above solvent (E) is not particularly limited, and various organic solvents used in the relevant technical field can be used.

[0188] Specific examples of the above 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 alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate; alkylene glycol alkyl ether acetates 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; Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, and butoxybutyl alcohol; Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, 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, butyl 2-methoxypropionate, 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-methoxypropionate, ethyl 3-methoxypropionate, Esters such as propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, etc.; cyclic ethers such as tetrahydrofuran and pyran;Examples include cyclic esters such as γ-butyrolactone. The solvents (E) exemplified here may be used alone or in combination of two or more.

[0189] When considering the applicability and drying properties, the above solvent (E) can preferably be used as an ester such as diethylene glycol dialkyl ether, alkylene glycol alkyl ether acetate, ketone, butanediol alkyl ether acetate, butanediol monoalkyl ether, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc., and more preferably, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. can be used.

[0190] The above solvent may be included in an amount of 90 to 97 wt% based on 100 wt% of the total resin composition for an anti-reflection film. When the content of the solvent is within the above range, the coating property becomes good when applied using a coating device such as a spin coater, a slit and spin coater, a slit coater (also sometimes called a die coater or curtain flow coater), or an inkjet, which is preferable.

[0191]

[0192] The resin composition for an anti-reflection film according to one embodiment of the present invention may further include a leveling agent.

[0193] As the leveling agent, a commercially available surfactant can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants, and these may be used singly or in combination of two or more.

[0194] Examples of the 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. As for the fluorine-based surfactants, examples of commercially available products include Megapak F-470, F-471, F-475, F-482, F-489, and F-554 from Dainippon Ink & Chemical Industry Co., Ltd.

[0195] The above leveling agent may be included in an amount of 0.0001 to 0.01 wt% based on 100 wt% of the total resin composition for an anti-reflection film. When the content of the leveling agent is within the above range, the film-forming property of the resin composition for an anti-reflection film is excellent, and the flatness of the film formed therefrom is improved, which is preferable.

[0196]

[0197] The resin composition for an antireflection film according to one embodiment of the present invention may further include, in addition to the above-described components, additives such as a curing agent, a slip improving agent, an adhesion accelerator, an antioxidant, an ultraviolet absorber, an anti-coagulant, a radical generator, and a photoacid generator, as needed.

[0198] The above hardener is used to increase deep hardening and mechanical strength, and specific examples of the hardener include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

[0199] Specific examples of the epoxy compound in the above curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene (co)polymer epoxides, glycidyl (meth)acrylate (co)polymers, triglycidyl isocyanurate, etc.

[0200] Specific examples of the oxetane compound in the above curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

[0201] The above curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Examples of the above curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators.

[0202] The above carboxylic anhydride can be used as an epoxy resin curing agent commercially available. Examples of the above epoxy resin curing agent include (Adekahadona EH-700) (manufactured by Adeka Kogyo Co., Ltd.), (Rikasido HH) (manufactured by Shin Nippon Eka Co., Ltd.), and (MH-700) (manufactured by Shin Nippon Eka Co., Ltd.). The curing agents exemplified above can be used alone or in combination of two or more.

[0203] Examples of the above slip improvement agent include commercially available products such as BYK-333 (BYK).

[0204] As the adhesion accelerator, a silane compound is preferable, and specific examples thereof 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-isocyanatepropyltriethoxysilane.

[0205] Specifically, the antioxidants include 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenylacrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepin, 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), 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-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, Examples include 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2,6-di-tert-butyl-4-methylphenol.

[0206] Specific examples of the above ultraviolet absorbent include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, etc.

[0207] Specific examples of the above anti-coagulant include sodium polyacrylate and the like.

[0208] Examples of the above radical generators include commercially available products such as OXE 01 (BASF).

[0209] Examples of the photoacid generators include commercially available products such as Irgacure 290 (BASF).

[0210]

[0211] One embodiment of the present invention relates to an antireflection film formed using the above-described resin composition for an antireflection film.

[0212] According to the present invention, the anti-reflection film can be manufactured by applying the above-described anti-reflection film resin composition onto a substrate and then applying heat.

[0213] A preferred example of the manufacturing process is to apply a resin composition for an anti-reflection film onto a substrate and then heat and dry it to remove volatile components such as solvents, thereby obtaining a smooth film.

[0214] The coating method may be, for example, spin coating, flexible coating, roll coating, slit and spin coating, or slit coating.

[0215] After application, heat drying (pre-baking) or after reduced pressure drying is performed to volatilize volatile components such as solvents. Here, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C.

[0216] Afterwards, exposure and development processes can be performed as needed.

[0217] Finally, a post-baking process is performed again to form a hardened network. The heating temperature is typically around 70 to 230°C. Heating methods such as a hot plate, clean oven, or infrared heater can be used. However, the present invention is not limited to these heating methods.

[0218] Using the resin composition for an antireflection film of the present invention, a cured film can be formed on a substrate through each of the above processes.

[0219] The cured film obtained in this way can be usefully used as an antireflection film for a solid-state imaging device.

[0220]

[0221] Accordingly, one embodiment of the present invention relates to a solid-state imaging device having the above-described anti-reflection film.

[0222] The solid-state imaging element may include, for example, a Charged Coupled Device (CCD) or Complementary Metal Oxide Semiconductor (CMOS) image sensor.

[0223] The above solid-state imaging device includes a support including a semiconductor device or a photoelectric conversion device and a micro lens, and the anti-reflection film can be formed on the micro lens.

[0224]

[0225] Hereinafter, the present invention will be described in more detail through examples, comparative examples, and experimental examples. These examples, comparative examples, and experimental examples are intended solely to illustrate the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not limited thereto.

[0226]

[0227] Synthesis Example 1: Synthesis of binder resin (C-1)

[0228] A nitrogen atmosphere was formed by supplying nitrogen at a flow rate of 0.02 L / min to a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and 150 g of diethylene glycol methyl ethyl ether was added and heated to 70°C while stirring. Next, 76.7 g (0.95 mol) of 3-diethoxymethylsilylpropyl methacrylate and a compound represented by the following chemical formula 1a-1 (molar ratio of 50:50) and 4.3 g (0.05 mol) of methacrylic acid were added and dissolved to prepare a solution.

[0229] [Chemical Formula 1a-1]

[0230]

[0231] The prepared solution was added dropwise into a flask using a dropping funnel, and then 27.9 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved in 200 g of diethylene glycol methyl ethyl ether and added dropwise into the flask through a separate dropping funnel over 4 hours. After the dropping of the polymerization initiator was completed, the solution was maintained at 70°C for 4 hours and then cooled to room temperature to obtain a binder resin solution. The weight average molecular weight (Mw) of the obtained binder resin (C-1) was 8,300 and the molecular weight distribution was 1.82.

[0232]

[0233] Synthesis Example 2: Synthesis of binder resin (C-2)

[0234] A binder resin solution was obtained by performing the same process as in Synthesis Example 1, except that the molar ratio of 3-diethoxymethylsilylpropyl methacrylate and the compound represented by Chemical Formula 1a-1 was changed to 95:5. The weight average molecular weight (Mw) of the obtained binder resin (C-2) was 8,600, and the molecular weight distribution was 1.86.

[0235]

[0236] Synthesis Example 3: Synthesis of binder resin (C-3)

[0237] A binder resin solution was obtained by performing the same process as in Synthesis Example 1, except that the molar ratio of 3-diethoxymethylsilylpropyl methacrylate and the compound represented by Chemical Formula 1a-1 was changed to 90:10. The weight average molecular weight (Mw) of the obtained binder resin (C-3) was 8,500, and the molecular weight distribution was 1.85.

[0238]

[0239] Synthesis Example 4: Synthesis of binder resin (C-4)

[0240] A binder resin solution was obtained by performing the same process as in Synthesis Example 1, except that the molar ratio of 3-diethoxymethylsilylpropyl methacrylate and the compound represented by the chemical formula 1a-1 was changed to 10:90. The weight average molecular weight (Mw) of the obtained binder resin (C-4) was 8,100, and the molecular weight distribution was 1.83.

[0241]

[0242] Synthesis Example 5: Synthesis of binder resin (C-5)

[0243] A binder resin solution was obtained by performing the same process as in Synthesis Example 1, except that the molar ratio of 3-diethoxymethylsilylpropyl methacrylate and the compound represented by the chemical formula 1a-1 was changed to 5:95. The weight average molecular weight (Mw) of the obtained binder resin (C-5) was 8,000, and the molecular weight distribution was 1.82.

[0244]

[0245] Synthesis Example 6: Synthesis of binder resin (C-6)

[0246] A binder resin solution was obtained by performing the same process as in Synthesis Example 1, except that a compound represented by the following chemical formula a was used instead of the compound represented by the chemical formula 1a-1 as a monomer. The weight average molecular weight (Mw) of the obtained binder resin (C-6) was 7,600, and the molecular weight distribution was 1.80.

[0247] [chemical formula a]

[0248]

[0249]

[0250] Manufacturing Example 1-1: Manufacturing of hollow aluminosilicate particles (A-1)

[0251] A core template for a hollow core was prepared by adding 0.172 g of polyacrylic acid, 0.086 g of polystyrene sulfonic acid, and 3 ml of ammonium hydroxide to a 1 L three-necked round flask, followed by the addition of 60 ml of ethanol. 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 including cores. After reacting the particles with 5% sodium hydroxide, they were washed with distilled water and alcohol, and dried to prepare hollow aluminosilicate particles. 20 g of the prepared particles and 80 g of distilled water were added and ultrasonically dispersed for 1 hour using an ultrasonic disperser to prepare an aqueous dispersion of aluminosilicate stably dispersed in water. This dispersion was placed in a 1 L hydrothermal reactor and reacted at 180°C for 10 hours, followed by precipitation and drying to produce hollow aluminosilicate particles with increased shell density. The solvent was replaced with propylene glycol monomethyl ether acetate to produce an aluminosilicate propylene glycol monomethyl ether acetate dispersion having a solid content of 10 wt%. The average particle diameter was 88 nm, and the Si / Al molar ratio was 12.

[0252]

[0253] Manufacturing Example 1-2: Manufacturing of hollow aluminosilicate particles (A-2)

[0254] A hollow aluminosilicate particle dispersion was obtained in the same manner as in Manufacturing Example 1-1, except that 20 ml of 3% aluminum isopropoxide was used. The average particle diameter was 84 nm, and the Si / Al molar ratio was 5.

[0255]

[0256] Manufacturing Example 1-3: Manufacturing of hollow aluminosilicate particles (A-3)

[0257] A hollow aluminosilicate particle dispersion was obtained in the same manner as in Manufacturing Example 1-1, except that 6 ml of 3% aluminum isopropoxide was used. The average particle diameter was 88 nm, and the Si / Al molar ratio was 16.

[0258]

[0259] Manufacturing Example 2-1: Manufacturing of surface-modified hollow aluminosilicate particles (F-1)

[0260] Surface-modified hollow aluminosilicate particles were prepared by applying the method of the paper Korean Chem. Eng. Res., Vol. 49, No. 2, April, 2011, pp. 181-186.

[0261] Specifically, the hollow aluminosilicate particles (A-1) manufactured in the above Manufacturing Example 1-1 were dried in a dry oven at 120°C for more than 3 hours, cooled to room temperature in a desiccator to remove adsorbed moisture, and then used. The solvent was made by adjusting the ratio of ethanol and deionized water to 80:20 (v / v%) at room temperature and pressure to make 300 ml, and then the pH was adjusted to 3 to 5 using acetic acid and stirred at 300 rpm for about 30 minutes using a magnetic stirrer. 25.0 g of the binder resin (C-1) synthesized in the above Synthesis Example 1 was added to the stirred solvent, and stirred at 300 rpm for 1 hour to hydrolyze the alkoxy group bonded to the Si terminal. After the hydrolysis reaction was completed, 5.0 g of the hollow aluminosilicate particles (A-1) from which the moisture had been removed were placed in a round flask and surface-modified 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 Scientific), and the supernatant was discarded. The particles were washed several times with an ethanol / deionized water (80:20 v / v%) solution and pure ethanol, centrifuged, and dried in a vacuum oven at 40°C for 24 hours to obtain surface-modified hollow aluminosilicate particles (F-1).

[0262]

[0263] Manufacturing Example 2-2: Manufacturing of surface-modified hollow aluminosilicate particles (F-2)

[0264] Surface-modified hollow aluminosilicate particles (F-2) were manufactured in the same manner as in Manufacturing Example 2-1, except that the binder resin (C-2) synthesized in Synthesis Example 2 was used instead of the binder resin (C-1) synthesized in Synthesis Example 1.

[0265]

[0266] Manufacturing Example 2-3: Manufacturing of surface-modified hollow aluminosilicate particles (F-3)

[0267] Surface-modified hollow aluminosilicate particles (F-3) were manufactured in the same manner as in Manufacturing Example 2-1, except that the binder resin (C-3) synthesized in Synthesis Example 3 was used instead of the binder resin (C-1) synthesized in Synthesis Example 1.

[0268]

[0269] Manufacturing Example 2-4: Manufacturing of surface-modified hollow aluminosilicate particles (F-4)

[0270] Surface-modified hollow aluminosilicate particles (F-4) were manufactured in the same manner as in Manufacturing Example 2-1, except that the binder resin (C-4) synthesized in Synthesis Example 4 was used instead of the binder resin (C-1) synthesized in Synthesis Example 1.

[0271]

[0272] Manufacturing Example 2-5: Manufacturing of surface-modified hollow aluminosilicate particles (F-5)

[0273] Surface-modified hollow aluminosilicate particles (F-5) were manufactured in the same manner as in Manufacturing Example 2-1, except that the binder resin (C-5) synthesized in Synthesis Example 5 was used instead of the binder resin (C-1) synthesized in Synthesis Example 1.

[0274]

[0275] Manufacturing Example 2-6: Manufacturing of surface-modified hollow aluminosilicate particles (F-6)

[0276] Surface-modified hollow aluminosilicate particles (F-6) were manufactured in the same manner as in Manufacturing Example 2-1, except that the binder resin (C-6) synthesized in Synthesis Example 6 was used instead of the binder resin (C-1) synthesized in Synthesis Example 1.

[0277]

[0278] Manufacturing Example 2-7: Manufacturing of surface-modified hollow aluminosilicate particles (F-7)

[0279] Surface-modified hollow aluminosilicate particles (F-7) were manufactured in the same manner as in Manufacturing Example 2-1, except that the hollow aluminosilicate particles (A-2) manufactured in Manufacturing Example 1-2 were used instead of the hollow aluminosilicate particles (A-1) manufactured in Manufacturing Example 1-1.

[0280]

[0281] Manufacturing Example 2-8: Manufacturing of surface-modified hollow aluminosilicate particles (F-8)

[0282] Surface-modified hollow aluminosilicate particles (F-8) were manufactured in the same manner as in Manufacturing Example 2-1, except that the hollow aluminosilicate particles (A-3) manufactured in Manufacturing Example 1-3 were used instead of the hollow aluminosilicate particles (A-1) manufactured in Manufacturing Example 1-1.

[0283]

[0284] Examples and Comparative Examples: Preparation of Resin Composition for Antireflection Film

[0285] A resin composition for an antireflection film was prepared by mixing each component according to the compositions in Tables 1 and 2 below (% by weight).

[0286]

[0287] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Surface-modified hollow aluminosilicate particles (F) F-1 2.0 2.0 2.0 2.0 2.0 2.0 F-2 F-3 2.0 2.0 F-4 2.0 2.0 F-5 F-6 F-7 F-8 Amorphous silica particles (B) B-1 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 B-2 Binder resin (C) C-1 0.6 0.6 0.6 C-2 C-3 0.6 0.6 0.6 C-4 0.6 0.6 0.6 C-5 C-6 Thermal polymerization initiator (D) D-10.1 0.10.10.10.10.10.1D-2 0.1 D-3 0.1 Solvent(E)E-195.095.095.095.095.095.095.095.095.0

[0288]

[0289] ClassificationComparative Example 1Comparative Example 2Comparative Example 3Comparative Example 4Comparative Example 5Comparative Example 6Comparative Example 7Comparative Example 8Comparative Example 9Comparative Example 10Surface-modified hollow aluminosilicate particles (F) F-1 2.02.02.02.02.0F-22.0 F-3 F-4 F-5 2.0 F-6 2.0 F-7 2.0F-8 2.0Amorphous silica particles (B) B-1 2.32.32.32.32.32.32.42.32.3B-22.3Binder resin (C) C-10.60.60.6 0.60.60.6C-2 0.6C-3 C-4 C-5 0.6C-6 0.6 Thermal polymerization Initiator (D) D-10.10.10.10.10.10.1 0.10.10.1D-2 D-3 Solvent (E) E-195.095.095.095.095.095.095.095.095.095.0

[0290]

[0291] F-1 to F-8: Surface-modified hollow aluminosilicate particles of Manufacturing Examples 2-1 to 2-8, respectively.

[0292] B-1: PM-09 (average particle size 22 nm, Tokuyama)

[0293] B-2: QSG-100 (average particle size 110 nm, Shin-Etsu Chemical)

[0294] C-1 to C-6: Binder resins synthesized in Synthesis Examples 1 to 6, respectively.

[0295] D-1: V-601 (Wakosa)

[0296] D-2: V-59 (Wakosa)

[0297] D-3: V-65 (Wako)

[0298] E-1: Propylene glycol monomethyl ether acetate

[0299]

[0300] Experimental example:

[0301] Using the resin composition for an antireflection film manufactured in the above examples and comparative examples, an antireflection film was manufactured as follows, and the physical properties of the antireflection film were evaluated by the following method, and the results are shown in Tables 3 and 4 below. In addition, the a / b values ​​were calculated and shown in Tables 3 and 4. Here, a is the average particle diameter of hollow aluminosilicate particles, and b is the average particle diameter of amorphous silica particles.

[0302]

[0303] <Anti-reflective film manufacturing>

[0304] The antireflection film resin compositions manufactured in the above examples and comparative examples were each spin-coated on a 4-inch silicon wafer (manufactured by SK Siltron), and then pre-baked at 100°C for 60 seconds using a hot plate. The pre-baked substrate was cooled to room temperature and then post-baked in an oven at 200°C for 300 seconds. The thickness of the cured film was 100 nm.

[0305]

[0306] (1) Refractive index measurement

[0307] For the above-mentioned manufactured cured film substrate, 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 25°C and 50%RH, applying incident angles of 65, 70, and 75°. The measured linear polarization measurement data (Ellipsometry data(Ψ, Δ)) was optimized (fitted) to the Cauchy model of the following mathematical equation 1 using Complete EASE software so that the MSE was 20 or less, and the refractive index at a wavelength of 550 nm was calculated.

[0308] [Mathematical Formula 1]

[0309]

[0310]

[0311] In the above mathematical expression 1, 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.

[0312]

[0313] (2) Crack resistance

[0314] A cured film substrate was manufactured in the same manner as the above manufacturing method, except that the thickness of the cured film was formed to 500 nm.

[0315] The surface of the above-mentioned cured film substrate was observed to check for cracks, and the crack resistance was evaluated according to the following evaluation criteria.

[0316] <Evaluation Criteria>

[0317] ○: No cracks occur

[0318] ×: Cracks occur

[0319]

[0320] (3) Flatness of the film

[0321] The Ra value of the cured film substrate manufactured above was measured using an atomic force microscope (AFM) Nanoscope (Blucar AXS), and the flatness of the film was evaluated according to the following evaluation criteria.

[0322] <Evaluation Criteria>

[0323] ◎: Ra value less than 6 nm

[0324] ○: Ra value is 6 nm or more and less than 9 nm

[0325] ×: Ra value is 9 nm or more

[0326]

[0327] (4) Moisture permeability at high temperature and high humidity

[0328] The refractive index of the cured film substrate manufactured above was measured before and after 500 hours of storage in a constant temperature and humidity chamber PR-1J (ESPEC) at a temperature of 85°C and a humidity of 85%, and the change in refractive index was calculated using the following mathematical formula 2, and the moisture permeability at high temperature and high humidity was evaluated according to the following evaluation criteria.

[0329] [Equation 2]

[0330] Refractive index change = [(refractive index after storage - refractive index before storage) / refractive index before storage] × 100

[0331] <Evaluation Criteria>

[0332] ◎: less than 1%

[0333] ○: 1% or more but less than 5%

[0334] ×: 5% or more

[0335]

[0336] (5) Permeability to developing solution and stripping solution

[0337] The refractive index of the above-manufactured cured film substrate was measured before and after immersion in 2.38% tetramethylammonium hydroxide (TMAH) (developer) and methylpyrrolidone (stripping agent) for 5 minutes, respectively, and the change in refractive index was calculated using the following mathematical formula 3, and the moisture permeability for the developer and stripping agent was evaluated according to the following evaluation criteria.

[0338] [Equation 3]

[0339] Refractive index change = [(refractive index after immersion - refractive index before immersion) / refractive index before immersion] × 100

[0340] <Evaluation Criteria>

[0341] ◎: less than 1%

[0342] ○: 1% or more but less than 5%

[0343] ×: 5% or more

[0344]

[0345] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Si / Al ratio 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 a / b value 4 4 ​​4 4 4 4 4 4 4 Refractive index 1.26 1.28 1.27 1.30 1.29 1.32 1.33 1.32 1.30 Crack resistance ○○○○○○○○○ Flatness ◎◎◎○○○○○○ High temperature and high humidity moisture permeability ◎◎◎○◎○○○○ Developer moisture permeability ◎◎◎○◎○○○○ Strippermeability ◎◎◎○◎○○○○

[0346]

[0347] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Si / Al ratio 12 12 12 12 12 12 12 12 12 5 16 12 a / b value 4 4 ​​4 4 4 4 4 3.8 4 0.8 Refractive index 1.3 4 1.3 2 1.3 3 1.2 9 1.2 9 1.3 0 1.2 7 1.4 2 1.4 0 1.4 8 Crack resistance ○○×○○×××××× Flatness ○○×○○××××× High temperature and high humidity moisture permeability ○○××○×××××× Developer moisture permeability ×××××××○○○ Strippermeability ×××××××○○○

[0348]

[0349] As shown in Tables 3 and 4 above, it was confirmed that the resin composition for an antireflection film comprising hollow aluminosilicate particles having a Si / Al molar ratio of 7 to 15 and a surface modified with a second binder resin having a curable functional group and a hydrolyzable silyl group, and a first binder resin having a curable functional group and a hydrolyzable silyl group, according to the present invention, suppresses the occurrence of cracks during film formation, has excellent flatness of the film, prevents moisture adsorption under high temperature and high humidity, and can block moisture penetration by a developer and a stripper.

[0350] On the other hand, the antireflection film resin compositions of Comparative Examples 1 to 10 were found to cause cracks during film formation, have poor film flatness, allow moisture to pass through under high temperature and high humidity, or allow moisture to pass through from a developer and stripper.

[0351] Specifically, the antireflection film resin compositions of Comparative Examples 3 and 6, which included a binder resin having no curable functional group or hollow aluminosilicate particles surface-modified with such a binder resin, exhibited cracks during film formation, and the flatness, high-temperature and high-humidity moisture permeability, and developer and strippermeability of the film were all poor. In addition, the antireflection film resin composition of Comparative Example 7, which did not include a thermal polymerization initiator, also exhibited cracks during film formation, and the flatness, high-temperature and high-humidity moisture permeability, and developer and strippermeability of the film were all poor. In addition, the antireflection film resin compositions of Comparative Examples 8 and 9, in which the Si / Al molar ratio was outside the range of 7 to 15, and Comparative Example 10, in which the a / b value was less than 3, exhibited good developer and strippermeability, but poor crack resistance, flatness, and high-temperature and high-humidity moisture permeability of the film. In particular, the antireflection film resin compositions of Comparative Examples 1, 2, 4 and 5, which include a binder resin in which the molar ratio of a repeating unit having a curable functional group and a repeating unit having a hydrolyzable silyl group is outside a specific range, or which include hollow aluminosilicate particles surface-modified with such a binder resin, had poor developer and strippermeability.

[0352]

[0353] While specific aspects of the present invention have been described in detail above, it should be apparent to those skilled in the art that these specific descriptions are merely preferred embodiments and do not limit the scope of the present invention. Those skilled in the art will be able to make various applications and modifications within the scope of the present invention based on the above description.

[0354] Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims

1. Comprising hollow aluminosilicate particles, amorphous silica particles, a first binder resin having a curable functional group and a hydrolyzable silyl group, a thermal polymerization initiator, and a solvent, A resin composition for an antireflection film, wherein the hollow aluminosilicate particles have a Si / Al molar ratio of 7 to 15 and the surface is modified with a second binder resin having a curable functional group and a hydrolyzable silyl group.

2. In the first paragraph, a resin composition for an anti-reflection film satisfying the following mathematical formula 1: [Mathematical Formula 1] 3 ≤ 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.

3. A resin composition for an antireflection film in the first paragraph, wherein the average particle diameter of the hollow aluminosilicate particles is 30 to 150 nm.

4. In the first paragraph, the first binder resin and the second binder resin each independently comprise a repeating unit represented by the following chemical formula 1 and a repeating unit represented by the following chemical formula 2: [Chemical Formula 1] [Chemical Formula 2] In the above formula, R 1 , R 3 and R 4 are each independently a hydrogen atom or a methyl group, R 2 is a residue containing a carboxylic acid derived by a hydrogen atom or an acid anhydride, L 1 does not exist or C1-C 10 alkylene group or C1-C 10 is an oxyalkylene group, R 5 is a hydroxy group, a C1-C4 alkoxy group or halogen, R 6 is a hydrogen atom or C1-C 20 is an alkyl group, n is an integer from 1 to 3.

5. In the fourth paragraph, the first binder resin and the second binder resin each independently further comprise a repeating unit represented by the following chemical formula 3: [Chemical Formula 3] In the above formula, R 7 is a hydrogen atom or a methyl group, L 2 does not exist or C1-C 18 is an alkylene group.

6. A resin composition for an antireflection film in the fourth paragraph, wherein the molar ratio of the repeating unit represented by the chemical formula 1 and the repeating unit represented by the chemical formula 2 is 10:90 to 90:

10.

7. A resin composition for an anti-reflection film, wherein the repeating unit represented by the chemical formula 3 in the fifth paragraph is included in an amount of 1 to 30 mol% based on 100 mol% of the total repeating units constituting the binder resin.

8. A resin composition for an anti-reflection film further comprising a leveling agent in the first paragraph.

9. In the first paragraph, the cured film formed from the resin composition for an anti-reflection film has a refractive index of 1.20 to 1.35 at 550 nm.

10. An anti-reflection film formed using a resin composition for an anti-reflection film according to any one of claims 1 to 9.

11. A solid-state imaging device having an anti-reflection film according to Article 10.

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