Thermosetting resin composition, cured film, and solid-state imaging device

Abstract

The present invention provides a thermosetting resin composition comprising a binder resin, a thermal initiator, a thermosetting agent, and a solvent, wherein the binder resin comprises an acrylic copolymer including a repeating unit having a carbazole group and a repeating unit having a glycidyl group; a cured film comprising the thermosetting resin composition; and a solid-state imaging device comprising the cured film. The thermosetting resin composition of the present invention can be baked within a few minutes at a temperature of 220°C or less and can form a cured film having high transmittance and high refractive index, excellent flatness and hardness, and no coating unevenness. Furthermore, the thermosetting resin composition of the present invention has excellent stability over time and dry etching resistance, which is advantageous for realizing microlens shapes.

Description

[Technical Field]

[0001] The present invention relates to a thermosetting resin composition, a cured film, and a solid-state imaging device, and more particularly to a thermosetting resin composition that can be baked within a few minutes at a temperature of 220°C or less, has high transmittance and high refractive index, and is excellent in flatness and hardness, has no coating unevenness, and has excellent stability over time and physical properties that are advantageous for realizing a microlens shape; a cured film made of the thermosetting resin composition; and a solid-state imaging device including the cured film. [Background technology]

[0002] A solid-state imaging device converts an image captured using optical energy into electrical information and may include a color filter below the lens. For example, a CMOS image sensor (CIS) uses fine-pitch color filters patterned at a higher resolution than the color filters corresponding to the pixels of a typical display device. The color filters of a CIS usually have a color pattern of the three primary colors, red (R), green (G), and blue (B), and are responsible for separating transmitted light into the three primary colors.

[0003] An organic protective film, that is, an overcoat film, is provided on the color filter of such a CIS to flatten the steps of the RGB colored pattern.

[0004] Since the overcoat film is formed directly on the RGB colored pattern, it must be baked at a low temperature for a short time to minimize deterioration of the RGB colored pattern.

[0005] Korean Patent Publication No. 10-2006-0036611 discloses a thermosetting resin composition for forming a protective film, which contains bisphenol A-type alcohols that act as crosslinkers for acrylic resins containing carboxyl groups or epoxy groups, and methacrylates or epoxies derived from the alcohols; or phenols.

[0006] However, the thermosetting resin composition has a drawback in that it requires baking at 220° C. for several tens of minutes.

[0007] Therefore, there is a need for technological development relating to a thermosetting resin composition that can be baked at a low temperature in a short time.

[0008] Furthermore, technological development is also required for thermosetting resin compositions that have high transmittance and high refractive index when cured, and that are excellent in flatness and hardness and do not cause coating unevenness, so as to be suitable for overcoat films.

[0009] On the other hand, microlenses that focus incident light to the center are formed on the overcoat film to improve CIS efficiency, and therefore a thermosetting resin composition for forming an overcoat film that exhibits properties advantageous for forming the microlenses is required.

[0010] Furthermore, such a thermosetting resin composition is required to have stability over time, so that the composition does not change even when stored for a long period of time. Summary of the Invention [Problem to be solved by the invention]

[0011] An object of the present invention is to provide a thermosetting resin composition that can be baked within a few minutes at a temperature of 220°C or less, has high transmittance and high refractive index, is excellent in flatness and hardness, has no coating unevenness, is stable over time, and has physical properties that are advantageous for realizing a microlens shape.

[0012] Another object of the present invention is to provide a cured film made from the above thermosetting resin composition.

[0013] It is still another object of the present invention to provide a solid-state imaging device including the cured film. [Means for solving the problem]

[0014] On the other hand, the present invention provides a thermosetting resin composition comprising a binder resin, a thermal initiator, a thermal curing agent, and a solvent, The binder resin provides a thermosetting resin composition containing an acrylic copolymer including a repeating unit having a carbazole group and a repeating unit having a glycidyl group.

[0015] In one embodiment of the present invention, the repeating unit having a carbazole group may be represented by the following Chemical Formula 1:

[0016] [ka]

[0017] In one embodiment of the present invention, the repeating unit having a glycidyl group may be represented by the following Chemical Formula 2:

[0018] [ka]

[0019] In the above formula, R a is hydrogen or a methyl group, L 1 does not exist or C1-C 10 or an alkylene group of C1-C 10 is an oxyalkylene group of the formula:

[0020] In one embodiment of the present invention, the repeating unit having a carbazole group may be contained in an amount of 25 to 50 mol % relative to 100 mol % of all repeating units constituting the binder resin.

[0021] In one embodiment of the present invention, the repeating unit having a glycidyl group may be contained in an amount of 10 to 30 mol % relative to 100 mol % of all repeating units constituting the binder resin.

[0022] In one embodiment of the present invention, the binder resin may be contained in an amount of 10 to 30% by weight relative to 100% by weight of the entire thermosetting resin composition.

[0023] In one embodiment of the present invention, the thermal initiator may include one or more compounds represented by the following formulas 3 to 5:

[0024] [ka]

[0025] In the above formula, R 1 is C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20 Cycloalkyl groups, C2-C 20 Heterocycloalkyl groups of C6-C 20 or an aryl group of C5-C 20 is a heteroaryl group of the formula: R 2 is C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20 Cycloalkyl groups, C2-C 20 Heterocycloalkyl groups of C6-C 20 or an aryl group of C5-C 20 is a heteroaryl group of the formula: R 1 and R 2 are each independently a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, -SO3M, -CO2M, a hydroxy group, a formyl group, an amino group, or a C1-C 20 and optionally substituted with an alkyl group of the formula: M represents a metal ion; R 3 and R 4 are C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20 Cycloalkyl groups, C2-C 20Heterocycloalkyl groups of C6-C 20 or an aryl group of C5-C 20 is a heteroaryl group of the formula: R 5 is a hydrogen atom, halogen atom, hydroxy group, thioether group, C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20 or a cycloalkyl group of C2-C 20 is a heterocycloalkyl group of the formula: R 6 ~R 9 are C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20 Cycloalkyl groups, C2-C 20 Heterocycloalkyl groups of C6-C 20 Aryl groups, C5-C 20 or a heteroaryl group of C6-C 20 is an aralkyl group of the formula: X - PF6 - , AsF6 - , SbF6 - , (CF3)2PF4 - , (CF3)3PF3 - , (CF3)4PF2 - , (CF3)5PF - , (CF3)6P - , (C2F5SO2)2N - , (CF3SO3)2N - , (CF3SO2)(CF3CO)N - , CF3CF2(CF3)2CO - , (CF3SO2)2CH - , (SF5)3C - , (CF3SO2)3C - , CF3COO - , CF3SO3 - , (C6F5)4B - or C3F7COO - is.

[0026] In one embodiment of the present invention, the thermal initiator may be included in an amount of 0.1 to 1.0 wt % based on 100 wt % of the total thermosetting resin composition.

[0027] In one embodiment of the present invention, the thermal curing agent may include an amine-based curing agent.

[0028] In one embodiment of the present invention, the thermal curing agent may include a compound represented by the following Formula 6:

[0029] [ka]

[0030] In the above formula, R 10 ~R 13 are each independently hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C2-C4 alkoxyalkyl group, or a thiol group; R 14 and R 15 are each independently hydrogen, a C1-C4 alkyl group, or an aryl group.

[0031] In one embodiment of the present invention, the thermosetting agent may be contained in an amount of 0.2 to 2.0% by weight based on 100% by weight of the total thermosetting resin composition.

[0032] On the other hand, the present invention provides a cured film made of the thermosetting resin composition.

[0033] In one embodiment of the present invention, the cured film may be an overcoat film, a microlens, or an overcoat film that doubles as a microlens.

[0034] On the other hand, the present invention provides a solid-state imaging device including the cured film. [Effects of the Invention]

[0035] The thermosetting resin composition according to the present invention can be baked within a few minutes at a temperature of 220°C or less, and can form a cured film having high transmittance and high refractive index, excellent flatness and hardness, and no coating unevenness. Furthermore, the thermosetting resin composition according to the present invention has excellent stability over time and properties, particularly dry etching resistance, that are advantageous for realizing a microlens shape. DETAILED DESCRIPTION OF THE INVENTION

[0036] The present invention will now be described in more detail.

[0037] One embodiment of the present invention relates to a thermosetting resin composition comprising a binder resin (A), a thermal initiator (B), a thermosetting agent (C), and a solvent (D), wherein the binder resin (A) comprises an acrylic copolymer including a repeating unit having a carbazole group and a repeating unit having a glycidyl group.

[0038] A thermosetting resin composition according to one embodiment of the present invention includes an acrylic copolymer containing a repeating unit having a carbazole group and a repeating unit having a glycidyl group as a binder resin, and also includes a thermal initiator and a thermosetting agent. This allows the composition to be baked at a temperature of 220°C or less within a few minutes, and can form a cured film that has high transmittance and high refractive index, excellent flatness and hardness, and is free from coating unevenness. Therefore, the thermosetting resin composition can be usefully used in the manufacture of an organic protective film, i.e., an overcoat film, that flattens steps in color filters used in image sensors.

[0039] In addition, the thermosetting resin composition according to one embodiment of the present invention has excellent stability over time and dry etching resistance that is advantageous for realizing a microlens shape by using a thermal initiator with a specific structure.

[0040] Typically, microlenses are formed by forming a pattern on an overcoat film using a photoresist and then reflowing the photoresist at high temperature to form a lens shape. However, when a cured film made of a thermosetting resin composition according to an embodiment of the present invention is applied as an overcoat film under the microlenses, the shape of the upper microlenses is transferred to the lower overcoat film by a dry etching process using a gas after the reflow process, and the overcoat film has a microlens shape, so that the overcoat film can also function as a microlens.

[0041] Binder resin (A) In one embodiment of the present invention, the binder resin (A) includes an acrylic copolymer containing a repeating unit having a carbazole group and a repeating unit having a glycidyl group. The binder resin (A) contains a repeating unit having a carbazole group and a repeating unit having a glycidyl group, which not only increases the refractive index of the cured film, but also improves the hardness and solubility of the cured film, but also improves the dry etching resistance.

[0042] The repeating unit having a carbazole group serves to increase the refractive index of the cured film.

[0043] The repeating unit having a carbazole group has a structure in which a carbazole group is introduced into the main chain in a pendant form.

[0044] Preferably, the repeating unit having a carbazole group may be represented by the following chemical formula 1.

[0045] [ka]

[0046] The repeating unit having a carbazole group may be introduced by using vinylcarbazole or the like as a monomer.

[0047] The repeating unit having a carbazole group may be contained in an amount of 25 to 50 mol %, preferably 30 to 40 mol %, relative to 100 mol % of all repeating units constituting the binder resin.

[0048] If the repeating unit having a carbazole group is contained in an amount of less than 25 mol %, the refractive index of the cured film may decrease, and if it is contained in an amount of more than 50 mol %, the hardness of the cured film may decrease.

[0049] The repeating unit having a glycidyl group serves to improve the hardness of the cured film and increase the solubility.

[0050] The repeating unit having a glycidyl group may have a structure in which a glycidyl group is introduced in a pendant form into the main chain.

[0051] Preferably, the repeating unit having a glycidyl group may be represented by the following chemical formula 2.

[0052] [ka]

[0053] In the above formula, R a is hydrogen or a methyl group, L 1 does not exist or C1-C 10 or an alkylene group of C1-C 10 is an oxyalkylene group of the formula:

[0054] As used herein, C1-C 10 The alkylene group in this case means 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, and n-nonylene.

[0055] As used herein, C1-C 10 The oxyalkylene group in this section refers to a functional group in which one or more carbon atoms in a linear or branched divalent hydrocarbon having 1 to 10 carbon atoms are substituted with oxygen, and examples thereof include, but are not limited to, oxymethylene, oxyethylene, oxypropylene, oxybutylene, oxypentylene, and oxyhexylene.

[0056] The repeating unit having a glycidyl group may be introduced using a (meth)acrylate having a glycidyl group as a monomer, for example, (oxiran-2-yl)methyl (meth)acrylate.

[0057] The repeating units having a glycidyl group may be contained in an amount of 10 to 30 mol %, preferably 15 to 25 mol %, based on 100 mol % of all repeating units constituting the binder resin. If the repeating units having a glycidyl group are contained in an amount less than 10 mol %, the hardness or solubility of the cured film may decrease, while if they are contained in an amount greater than 30 mol %, the refractive index of the cured film may decrease.

[0058] The binder resin (A) may further contain other repeating units in addition to the repeating units having a carbazole group and the repeating units having a glycidyl group described above.

[0059] Examples of the other repeating units include a repeating unit having a carboxyl group, a repeating unit having a hydroxyl group, a C1-C 10 Examples of the other repeating units include repeating units having an alkyl group and repeating units having an aryl group. In particular, the other repeating units may further include one or more repeating units having a hydroxy group and repeating units having an aryl group. The repeating units having a hydroxy group can improve the hardness and solubility of the cured film, and the repeating units having an aryl group can increase the solubility.

[0060] The repeating unit having a carboxyl group may be introduced using an ethylenically unsaturated monomer having a carboxyl group.

[0061] Specific examples of the ethylenically unsaturated monomer 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. Of these, acrylic acid and methacrylic acid are preferred.

[0062] The repeating unit having a hydroxy group may be introduced using an ethylenically unsaturated monomer having a hydroxy group, or may be introduced by further reacting the repeating unit having a carboxyl group with a compound having a glycidyl group.

[0063] Examples of the ethylenically unsaturated monomer having a hydroxy group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and N-hydroxyethyl acrylamide.

[0064] Examples of the compound having a glycidyl group include n-butyl glycidyl ether, propyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butylbenzoate, glycidyl stearate, allyl glycidyl ether, and glycidyl methacrylate, and two or more of these may be used in combination.

[0065] Said C1-C 10The repeating unit having an alkyl group of C1-C 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, and t-butyl (meth)acrylate. 10 These may be introduced using alkyl (meth)acrylate compounds, and two or more of these may be used in combination.

[0066] The repeating unit having an aryl group may be introduced using an aromatic vinyl compound such as styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, or p-vinylbenzyl glycidyl ether; or an aryl (meth)acrylate compound such as phenyl (meth)acrylate or benzyl (meth)acrylate, and two or more of these may be used in combination.

[0067] The binder resin (A) may be an N-substituted maleimide compound such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, or Np-methoxyphenylmaleimide; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 2-dicyclopentanyloxyethyl (meth)acrylate, or isobornyl and alicyclic (meth)acrylate compounds such as methyl (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 carboxylic acid ester compounds such as vinyl acetate and vinyl propionate; and vinyl cyanide compounds such as (meth)acrylonitrile and α-chloroacrylonitrile.

[0068] The other repeating units may be contained as the remainder so that the total amount of repeating units constituting the binder resin is 100 mol %.

[0069] The method for producing the copolymer is not particularly limited, and any conventionally known polymerization method may be used, among which solution polymerization is preferred. The polymerization temperature and polymerization time vary depending on the type and ratio of the monomers introduced, and the molecular weight and acid value of the desired alkali-soluble resin, but may be, for example, polymerized at 60 to 130°C for 1 to 10 hours.

[0070] When a solvent is used during the polymerization, a solvent typically used during radical polymerization reactions may be used, 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. These solvents may be used alone or in combination of two or more.

[0071] The polymerization initiator used in the polymerization may be any commonly used polymerization initiator and is not particularly limited. Specific examples include organic peroxides such as diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, and t-butyl peroxy-2-ethylhexanoate; and nitrogen compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl 2,2'-azobis(2-methylpropionate). These may be used alone or in combination of two or more.

[0072] During the polymerization, a chain transfer agent may be used to control the molecular weight and molecular weight distribution of the copolymer, such as a mercapto compound such as n-dodecanethiol, mercaptoacetic acid, or methyl mercaptoacetate; α-methylstyrene dimer, or the like.

[0073] The binder resin (A) may have a polystyrene-equivalent weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") of 5,000 to 30,000, preferably 10,000 to 20,000, as measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent).

[0074] The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A) may be 1.0 to 6.0, preferably 1.3 to 4.0.

[0075] When the weight average molecular weight and molecular weight distribution of the binder resin (A) are within the above ranges, the coating film has improved hardness and excellent adhesion.

[0076] The binder resin (A) may be contained in an amount of 10 to 30 wt %, preferably 15 to 25 wt %, based on 100 wt % of the total thermosetting resin composition. If the content of the binder resin is outside this range, the smoothness and hardness of the coating film may decrease and unevenness may occur on the coating surface. Specifically, if the content of the binder resin is less than this range, the solvent content may be relatively high, reducing the viscosity of the composition and resulting in a decrease in smoothness and a decrease in refractive index. Conversely, if the content of the binder resin is greater than this range, the solvent content may be relatively low, causing aggregation of the thermosetting agent, resulting in a decrease in smoothness.

[0077] Thermal initiator (B) In one embodiment of the present invention, the thermal initiator (B) can be sufficiently cured even by a low-temperature baking process of 220°C or less, preferably 180°C or less, and serves to improve the adhesion and transmittance of the overcoat film (protective film) formed using the same.

[0078] The thermal initiator (B) is a compound that generates an acid, such as a sulfonic acid, upon exposure to heat. The acid generated by heat triggers a curing reaction between the functional groups of the binder resin and the thermosetting agent. Furthermore, while functioning as a thermal initiator, it can form a cured film with high transmittance without affecting the transmittance of the thermosetting resin composition.

[0079] The thermal initiator may include one or more of the compounds represented by the following formulas 3 to 5.

[0080] [ka]

[0081] In the above formula, R 1 is C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20 Cycloalkyl groups, C2-C 20 Heterocycloalkyl groups of C6-C 20 or an aryl group of C5-C 20 is a heteroaryl group of the formula: R 2 is C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20 Cycloalkyl groups, C2-C 20 Heterocycloalkyl groups of C6-C 20 or an aryl group of C5-C 20 is a heteroaryl group of the formula: R 1 and R 2 are each independently a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, -SO3M, -CO2M, a hydroxy group, a formyl group, an amino group, or a C1-C 20 and optionally substituted with an alkyl group of the formula: M represents a metal ion; R 3 and R 4 are C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20 Cycloalkyl groups, C2-C 20 Heterocycloalkyl groups of C6-C 20 or an aryl group of C5-C 20 is a heteroaryl group of the formula: R 5 is a hydrogen atom, halogen atom, hydroxy group, thioether group, C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20or a cycloalkyl group of C2-C 20 is a heterocycloalkyl group of the formula: R 6 ~R 9 are C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20 Cycloalkyl groups, C2-C 20 Heterocycloalkyl groups of C6-C 20 Aryl groups, C5-C 20 or a heteroaryl group of C6-C 20 is an aralkyl group of the formula: X - PF6 - , AsF6 - , SbF6 - , (CF3)2PF4 - , (CF3)3PF3 - , (CF3)4PF2 - , (CF3)5PF - , (CF3)6P - , (C2F5SO2)2N - , (CF3SO3)2N - , (CF3SO2)(CF3CO)N - , CF3CF2(CF3)2CO - , (CF3SO2)2CH - , (SF5)3C - , (CF3SO2)3C - , CF3COO - , CF3SO3 - , (C6F5)4B - or C3F7COO - is.

[0082] As used herein, C1-C 30The alkyl group in this case means a straight-chain or branched hydrocarbon having 1 to 30 carbon atoms, and includes, but is not limited to, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, 2-ethylheptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl, nonadecyl, eicosanyl, and behenyl.

[0083] As used herein, C2-C 30 The alkenyl group means a straight-chain or branched unsaturated hydrocarbon having 2 to 30 carbon atoms and one or more carbon-carbon double bonds, and examples thereof include, but are not limited to, ethylenyl, propenyl, butenyl, and pentenyl.

[0084] As used herein, C3-C 20 The cycloalkyl group means a monocyclic or fused ring hydrocarbon having 3 to 20 carbon atoms, and examples thereof include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0085] As used herein, C2-C 20 The heterocycloalkyl group refers to a functional group in which one or more ring carbon atoms of a monocyclic or fused hydrocarbon having 2 to 20 carbon atoms are substituted with oxygen, sulfur, or nitrogen, and examples thereof include, but are not limited to, thiazolidinyl, oxiranyl, and the like.

[0086] As used herein, C6-C 20The aryl group in the above formula includes both monovalent aromatic groups and their partially reduced derivatives. The aromatic group is a monocyclic or fused ring system having 6 to 20 carbon atoms. Representative examples of the aryl group include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, pyrenyl, fluorenyl, diphenylfluorenyl, dinaphthalenylfluorenyl, carbazolyl, and biphenyl.

[0087] As used herein, C5-C 20 The heteroaryl group includes both monovalent heteroaromatic groups and their partially reduced derivatives. The heteroaromatic group is a monocyclic or fused ring system having 5 to 20 carbon atoms and containing one or more oxygen, sulfur, or nitrogen atoms. Representative examples of heteroaryl groups include, but are not limited to, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, oxazolinyl, and thiazolyl.

[0088] As used herein, C1-C 20 The alkyl group in the above expression means a linear or branched monovalent hydrocarbon group having 1 to 20 carbon atoms, and includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, 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, and n-decyl.

[0089] In this specification, the metal ions refer to alkali metal or alkaline earth metal ions.

[0090] As used herein, a thioether group is a group of formula -SR, where R is a C-C 30 and the like, but are not limited to methylthio, ethylthio, and the like.

[0091] As used herein, C6-C 20 The aralkyl group (aralkyl group) means a composite group having 6 to 20 carbon atoms formed by substituting an aryl group (aromatic hydrocarbon group) for a carbon atom of an alkyl group, and examples thereof include, but are not limited to, benzyl and phenethyl.

[0092] Preferably, X - is CF3SO3 - is.

[0093] The compounds represented by Chemical Formulas 3 to 5 may have a decomposition initiation temperature of less than 200°C, for example, 100°C or higher but lower than 200°C, preferably 150°C or higher but lower than 180°C. As a result, by using the compounds represented by Chemical Formulas 3 to 5 as thermal initiators, they can be sufficiently cured within a few minutes even when baked at a relatively low temperature of 220°C or lower. Furthermore, the compounds represented by Chemical Formulas 3 to 5 are advantageous in terms of dry etching resistance.

[0094] In particular, the compound represented by Chemical Formula 5 is advantageous in ensuring both stability over time and reliability because its reactivity with the binder resin and / or the thermosetting agent in the composition is reduced to an extent that does not affect reliability.

[0095] For example, the compound represented by Chemical Formula 3 includes one or more of the compounds represented by the following Chemical Formulas 3-1 to 3-3.

[0096] [ka]

[0097] Preferably, the compound represented by Chemical Formula 4 may be a compound represented by Chemical Formula 4a below.

[0098] [ka]

[0099] In the above formula, R 3 and R 4 are C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20 Cycloalkyl groups, C2-C 20 Heterocycloalkyl groups of C6-C 20 or an aryl group of C5-C 20 is a heteroaryl group of the formula: R 5 is a hydrogen atom, halogen atom, hydroxy group, thioether group, C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20 or a cycloalkyl group of C2-C 20 is a heterocycloalkyl group of the formula:

[0100] For example, examples of the compound represented by Chemical Formula 4 include (4-methylthiophenyl)methylphenylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate, diphenyl(4-hydroxyphenyl)sulfonium trifluoromethanesulfonate, and methylphenyl(4-hydroxyphenyl)sulfonium trifluoromethanesulfonate.

[0101] Preferably, the compound represented by Chemical Formula 5 may be a compound represented by Chemical Formula 5a below.

[0102] [ka]

[0103] In the above formula, R 6 ~R 9 are C1-C 30 Alkyl groups, C2-C 30 Alkenyl groups, C3-C 20 Cycloalkyl groups, C2-C 20 Heterocycloalkyl groups of C6-C 20 Aryl groups, C5-C 20 or a heteroaryl group of C6-C 20 is an aralkyl group of the formula:

[0104] Preferably, R 6 and R 7 are C1-C 30 is an alkyl group of the formula R 8 is C6-C 20 and R 9 is C6-C 20 The aralkyl group may be:

[0105] For example, the compound represented by Chemical Formula 5 includes the compound represented by Chemical Formula 5-1 below.

[0106] [ka]

[0107] The thermal initiator may be contained in an amount of 0.1 to 1.0 wt % relative to 100 wt % of the total thermosetting resin composition. When the thermal initiator is contained in this range, the solubility in solvents is improved and the thermosetting resin composition has high sensitivity, so that a cured film having excellent flatness can be formed.

[0108] Heat curing agent (C) In one embodiment of the present invention, the heat curing agent (C) is a component that undergoes a curing reaction with the functional group of the binder resin.

[0109] The heat curing agent may be an acid anhydride curing agent, an amine curing agent, a phenol curing agent, or the like, but from the viewpoint of improving productivity, adhesion, and dry etching resistance, an amine curing agent is preferred.

[0110] The amine-based curing agent may include a compound derived from a glycoluril structure, which may include a compound represented by the following Chemical Formula 6:

[0111] [ka]

[0112] In the above formula, R 10 ~R 13 are each independently hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C2-C4 alkoxyalkyl group, or a thiol group; R 14 and R 15 are each independently hydrogen, a C1-C4 alkyl group, or an aryl group.

[0113] As used herein, a C1-C4 alkyl group refers to a linear or branched monovalent hydrocarbon group having 1 to 4 carbon atoms, including, but not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and t-butyl.

[0114] As used herein, a C1-C4 alkoxy group refers to a linear or branched alkoxy group having 1 to 4 carbon atoms, including, but not limited to, methoxy, ethoxy, n-propanoxy, etc.

[0115] As used herein, the term "C2-C4 alkoxyalkyl group" refers to a composite group having 2 to 4 carbon atoms formed by substituting a linear or branched alkoxy group for a carbon atom of an alkyl group, and examples thereof include, but are not limited to, methoxymethyl, ethoxymethyl, and methoxyethyl.

[0116] As used herein, the term "aryl" includes both aromatic and heteroaromatic groups and their partially reduced derivatives. The aromatic group is a 5- to 15-membered monocyclic or fused ring, and the heteroaromatic group refers to an aromatic group containing one or more oxygen, sulfur, or nitrogen atoms. Representative examples of aryl groups include, but are not limited to, phenyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, oxazolyl, thiazolyl, and tetrahydronaphthyl.

[0117] Preferably, the compound represented by Chemical Formula 6 includes one or more of the compounds represented by the following Chemical Formulas 6-1 to 6-4.

[0118] [ka]

[0119] In the above formula, Pr is a propyl group, Ph is a phenyl group.

[0120] The compound represented by Chemical Formula 6 can improve stability by undergoing a curing reaction with the binder resin during post-baking. In addition, the compound represented by Chemical Formula 6 can maintain the spacing between the binder resins by penetrating into the spaces between the binder resins and curing, and N reacts with acid, thereby suppressing the occurrence of acid-induced unevenness and improving transmittance.

[0121] The thermosetting resin composition may contain the thermosetting agent in an amount of 0.2 to 2.0 wt % based on 100 wt % of the total thermosetting resin composition. When the thermosetting resin is contained in this range, the transmittance improving effect is maximized and a cured film with excellent adhesion can be formed.

[0122] Solvent (D) The solvent (D) is not particularly limited, and various organic solvents used in the art may be used.

[0123] 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 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 ethers such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate. Terephthalate acetates; 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, 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, 2-methoxypropionate 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-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Examples of the solvent (D) include esters such as ethyl, 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, and butyl 3-butoxypropionate; cyclic ethers such as tetrahydrofuran and pyran; and cyclic esters such as γ-butyrolactone. The solvents (D) exemplified here may be used alone or in combination of two or more.

[0124] In consideration of the coatability and drying property, the solvent (D) may preferably be an ester such as diethylene glycol dialkyl ethers, alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate, 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, or methyl 3-methoxypropionate.

[0125] The content of the solvent (D) may be 70% by weight or more, preferably 75 to 85% by weight, based on 100% by weight of the total thermosetting resin composition. If the content of the solvent is less than 70% by weight, the viscosity of the composition increases, reducing coatability, which may result in unevenness after coating and reduced flatness, resulting in problems such as the thermosetting resin composition not being applied uniformly.

[0126] Additive (E) In addition to the above components, the thermosetting resin composition according to one embodiment of the present invention may contain additives known in the art to the extent that the effects of the present invention are not impaired.

[0127] For example, a surfactant may be used to improve wetting, coating, and leveling properties.

[0128] The surfactants include silicone-based and fluorine-based surfactants, and commercially available products thereof include those manufactured by Sumitomo 3M Limited under the trade names of Fluorinert FC430 and Fluorinert FC431; those manufactured by Dainippon Ink and Chemicals, Inc. under the trade names of Megafac F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30, Megafac R08, Megafac R09, Megafac BL20, Megafac 475, Megafac 489, Megafac 544, and Megafac F443; and those manufactured by DIC Corporation under the trade names of F-430, F-510, F-554, F-563, R-40, R-41, and R-43.

[0129] The surfactant may be contained in an amount of 0.001 to 1.0% by weight, preferably 0.005 to 0.1% by weight, relative to 100% by weight of the entire thermosetting resin composition.

[0130] The thermosetting resin composition according to the present invention may be produced, for example, by adding the binder resin (A), the thermal initiator (B), the thermosetting agent (C), and other additives (E) used as needed to the solvent (D) and mixing them together, but the present invention is not limited to such a method.

[0131] The thermosetting resin composition produced as described above may be used after being filtered using a filter having a pore size of about 0.1 to 5 μm.

[0132] One embodiment of the present invention relates to a cured film made of the above-mentioned thermosetting resin composition.

[0133] According to the present invention, the cured film may be produced by applying the above-mentioned thermosetting resin composition to a substrate and then applying heat.

[0134] In a preferred example of the manufacturing process, the thermosetting resin composition is applied onto a substrate (usually glass) or onto a previously formed layer of the solid content of the resin composition, and then the composition is dried by heating to remove volatile components such as solvents, thereby obtaining a smooth coating film.

[0135] Examples of the coating method include spin coating, casting coating, roll coating, slit and spin coating, and slit coating.

[0136] After application, the coating is typically heated and cured at 220° C. or lower, preferably 180° C. or lower, for example, at a temperature of 100 to 180° C. for several minutes (approximately 3 minutes or less) to obtain the desired cured film.

[0137] The cured film thus obtained can be usefully used as an organic protective film, i.e., an overcoat film, that flattens steps in color filters used in image sensors such as CMOS image sensors.

[0138] Furthermore, the cured film can also function as a microlens for a solid-state imaging device, that is, the cured film may be an overcoat film that also functions as a microlens.

[0139] Specifically, a photoresist (PR) is applied onto the cured film and dried to obtain a coating film, which is then exposed and developed to form a pattern, and the pattern is reflowed by heat treatment to form a microlens pattern.Then, the underlying cured film is etched back using the microlens pattern as an etching mask, so that the shape of the microlens pattern can be transferred to the cured film.As a result, the cured film has the shape of a microlens and can also function as a microlens.

[0140] The thickness of the cured film may be 0.01 to 100 μm, preferably 0.05 to 10 μm, more preferably 0.1 to 3 μm, and even more preferably 0.2 to 1.5 μm.

[0141] Therefore, one embodiment of the present invention relates to a solid-state imaging device including the above-described cured film.

[0142] The solid-state imaging device may include a support including a semiconductor element or a photoelectric conversion element, and a microlens, and a color filter may be disposed between the support and the microlens.

[0143] The present invention will be described in more detail below with reference to examples, comparative examples, and experimental examples. Note that these examples, comparative examples, and experimental examples are merely for the purpose of illustrating the present invention, and it will be obvious to those skilled in the art that the scope of the present invention is not limited to these examples, comparative examples, and experimental examples.

[0144] Examples and Comparative Examples: Preparation of Thermosetting Resin Compositions Each component was mixed according to the composition shown in Tables 1 and 2 below, and then filtered through a Millipore filter with a pore size of 0.2 μm to prepare a thermosetting resin composition (unit: wt %).

[0145] [Table 1]

[0146] [Table 2]

[0147] (A-1) Binder resin: acrylic resin obtained by copolymerizing 0.38 mol of vinylcarbazole, 0.11 mol of 2-hydroxyethyl acrylate, 0.21 mol of glycidyl acrylate, and 0.30 mol of styrene, weight average molecular weight (Mw): 16,000 (A-2) Binder resin: acrylic resin obtained by copolymerizing 0.32 mol of vinylcarbazole, 0.28 mol of 2-hydroxyethyl acrylate, and 0.4 mol of styrene, weight average molecular weight (Mw): 14,000 (A-3) Binder resin: acrylic resin obtained by copolymerizing 0.3 mol of 2-hydroxyethyl acrylate, 0.3 mol of glycidyl acrylate, and 0.4 mol of styrene, weight average molecular weight (Mw): 3,700 (B-1) Thermal initiator: a compound represented by the following chemical formula 3-1

[0148] [ka]

[0149] (B-2) Thermal initiator: a compound represented by the following chemical formula 5-1

[0150] [ka]

[0151] (C) Heat curing agent: a compound represented by the following chemical formula 6-3

[0152] [ka]

[0153] (D-1) Solvent: 3-methoxybutanol (D-2) Solvent: Propylene glycol methyl ether acetate (E) Additive: surfactant, R-40 (DIC), 10% diluted solution Experimental Example: Cured films were prepared using the thermosetting resin compositions prepared in the above examples and comparative examples as described below. The physical properties of the thermosetting resin compositions and the cured films were evaluated by the following methods, and the results are shown in Tables 3 and 4 below.

[0154] <Production of cured film> About 2 ml of the thermosetting resin composition was applied onto a silicon wafer, and a coating film was formed using a spin coater.

[0155] The coating RPM was adjusted to target a coating thickness of 1.2 μm, and baking was completed on a hot plate at 180° C. for 180 seconds.

[0156] (1) Film Thickness The film thickness was measured at three points on a 6-inch silicon wafer as a reference, and the average value was calculated and used as the film thickness. The film thickness measuring device used was VM-1210 (manufactured by Dainippon Screen Mfg. Co., Ltd.).

[0157] (2) Flatness The film thickness was measured at 61 points on a 6-inch silicon wafer to determine the flatness, and then evaluated according to the following evaluation criteria. The film thickness was measured using a Filmetrics F-54 device.

[0158] <Evaluation criteria> ○: Less than 1% △: 1% or more but less than 2% ×: 2% or more (3) Transmittance A cured film was formed in the same manner as in the above-described method for producing a cured film, except that a glass substrate was used instead of a silicon wafer. Then, the transmittance for wavelengths from 200 nm to 800 nm was measured using a transmittance meter (Spectrophotometer, UV-2450), and the average in the visible light region (400 to 700 nm) was calculated.

[0159] (4) Coating unevenness The surface of the cured film was observed visually and under an optical microscope, and if there was no surface unevenness, it was marked with "O" and if there was, it was marked with "X".

[0160] (5) Refractive index Measurements were taken at three points using an Ellipsometer (Woollam, M-2000), and the average was calculated.

[0161] (6)Pencil hardness The hardness was measured from 3H to 4B using a motorized pencil hardness tester based on the ISO15184 evaluation method.

[0162] (7) Stability over time The initial film thickness of each of the thermosetting resin compositions prepared in the examples and comparative examples was measured, and the changes in film thickness were measured every week while storing these compositions at room temperature (23 to 25°C), and the stability over time was evaluated according to the following evaluation criteria.

[0163] Specifically, the film thickness was measured using a film thickness measuring device VM-1210 (manufactured by Dainippon Screen Mfg. Co., Ltd.) after dropping 1.8 μl of each composition onto a wafer, spin-coating at 1,800 rpm, and baking.

[0164] <Evaluation criteria> ○: No change in film thickness compared to the initial film thickness for 3 months or more △: Change in film thickness from the initial film thickness occurs within 1 month or more but less than 3 months ×: Change in film thickness from the initial film thickness occurs within a period of less than one month (8) Dry etching resistance The thermosetting resin compositions prepared in the examples and comparative examples were spin-coated onto silicon wafers to a dry thickness of 1.2 μm, and then baked at 220° C. for 180 seconds to prepare cured films, i.e., overcoat films.

[0165] A microlens photoresist was spin-coated onto the overcoat film to a dry thickness of 0.5 μm, baked at 100°C for 90 seconds, exposed to light, and developed to form a pattern. The pattern was then heat-treated at 146°C for 300 seconds for a reflow process, resulting in a microlens-shaped pattern.

[0166] The microlens-shaped pattern was dry etched at 15°C using a NeoGENII-MAXIS200 (manufactured by GigaLane) as a dry etching apparatus and C4F8, O2, and Ar as etching gases at the following flow rates, and the dry etching rate was measured. The dry etching resistance was evaluated according to the following evaluation criteria.

[0167] <Etching gas flow rate> C4F8:35sccm O2: 60sccm Ar: 200sccm <Evaluation criteria> ○: Less than 40Å / sec △: 40Å / sec or more and less than 50Å / sec ×:50Å / sec or more

[0168] [Table 3]

[0169] [Table 4]

[0170] As shown in Tables 3 and 4, the thermosetting resin compositions of Examples 1 to 7, which contain an acrylic copolymer containing a repeating unit having a carbazole group and a repeating unit having a glycidyl group as a binder resin according to the present invention, and which also contain a thermal initiator and a thermosetting agent, can be baked at a temperature of 220°C or less within a few minutes and can form a cured film that has high transmittance and high refractive index, excellent flatness and hardness, and is free from coating unevenness.

[0171] In particular, the thermosetting resin composition of Example 7, which contains the compound represented by Chemical Formula 5 as a thermal initiator, showed excellent stability over time and dry etching resistance suitable for realizing a microlens shape.

[0172] In contrast, the thermosetting resin compositions of Comparative Examples 1 to 4, which did not contain an acrylic copolymer containing a repeating unit having a carbazole group and a repeating unit having a glycidyl group as a binder resin, or which did not contain a thermal initiator or a thermal curing agent, showed results such as a decrease in transmittance and / or refractive index, and difficulty in simultaneously ensuring flatness, hardness, coating unevenness properties, stability over time, and dry etching resistance.

[0173] Although specific aspects of the present invention have been described in detail above, it will be apparent to those skilled in the art that such specific descriptions are merely preferred embodiments and are not intended to 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 content.

[0174] Therefore, the true scope of the invention is to be defined by the following claims and their equivalents.

Claims

1. A thermosetting resin composition comprising a binder resin, a thermal initiator, a thermal curing agent, and a solvent, The binder resin is a thermosetting resin composition comprising an acrylic copolymer including a repeating unit having a carbazole group and a repeating unit having a glycidyl group.

2. The thermosetting resin composition according to claim 1 , wherein the repeating unit having a carbazole group is represented by the following chemical formula 1: 【Chemistry 1】

3. The thermosetting resin composition according to claim 1 , wherein the repeating unit having a glycidyl group is represented by the following chemical formula 2: 【Chemistry 2】 In the above formula, R ａ is hydrogen or a methyl group, L １ does not exist or C １ -C １０ or an alkylene group of C １ -C １０ is an oxyalkylene group of the formula:

4. 2. The thermosetting resin composition according to claim 1, wherein the repeating unit having a carbazole group is contained in an amount of 25 to 50 mol % relative to 100 mol % of all repeating units constituting the binder resin.

5. 2. The thermosetting resin composition according to claim 1, wherein the repeating unit having a glycidyl group is contained in an amount of 10 to 30 mol % relative to 100 mol % of all repeating units constituting the binder resin.

6. 2. The thermosetting resin composition according to claim 1, wherein the binder resin is contained in an amount of 10 to 30% by weight relative to 100% by weight of the entire thermosetting resin composition.

7. The thermosetting resin composition according to claim 1, wherein the thermal initiator comprises one or more compounds represented by the following formulas 3 to 5: 【Transformation 3】 In the above formula, R １ is C １ -C ３０ alkyl group of C ２ -C ３０ an alkenyl group of C ３ -C ２０ a cycloalkyl group of C ２ -C ２０ a heterocycloalkyl group of C ６ -C ２０ or an aryl group of C ５ -C ２０ is a heteroaryl group of the formula: R ２ is C １ -C ３０ alkyl group of C ２ -C ３０ an alkenyl group of C ３ -C ２０ a cycloalkyl group of C ２ -C ２０ a heterocycloalkyl group of C ６ -C ２０ or an aryl group of C ５ -C ２０ is a heteroaryl group of the formula: R １ and R ２ are each independently a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, or —SO ３ M, -CO ２ M, a hydroxy group, a formyl group, an amino group, or C １ -C ２０ and optionally substituted with an alkyl group of the formula: M represents a metal ion; R ３ and R ４ are each independently C １ -C ３０ alkyl group of C ２ -C ３０ an alkenyl group of C ３ -C ２０ a cycloalkyl group of C ２ -C ２０ a heterocycloalkyl group of C ６ -C ２０ or an aryl group of C ５ -C ２０ is a heteroaryl group of the formula: R ５ represents a hydrogen atom, a halogen atom, a hydroxy group, a thioether group, C １ -C ３０ alkyl group of C ２ -C ３０ an alkenyl group of C ３ -C ２０ or a cycloalkyl group of C ２ -C ２０ is a heterocycloalkyl group of the formula: R ６ ~R ９ are each independently C １ -C ３０ alkyl group of C ２ -C ３０ an alkenyl group of C ３ -C ２０ a cycloalkyl group of C ２ -C ２０ a heterocycloalkyl group of C ６ -C ２０ an aryl group of C ５ -C ２０ or a heteroaryl group of C ６ -C ２０ is an aralkyl group of the formula: X － is PF ６ － , AsF ６ － , SbF ６ － , (CF ３ ) ２ PF ４ － , (CF ３ ) ３ PF ３ － , (CF ３ ) ４ [[ID=?]]PF ２ － , (CF ３ ) ５ PF － , (CF ３ ) ６ P － , (C ２ F ５ SO ２ ) ２ [[ID=?]]N － , (CF ３ SO ３ ) ２ N － , (CF ３ SO ２ )(CF ３ CO)N － , CF ３ CF ２ , (CF ３ ) ２ CO － , (CF ３ SO ２ ) ２ CH － , (SF ５ ) ３ C － , (CF ３ SO ２ ) ３ C － , CF ３ COO － , CF ３ SO ３ － , (C ６ F ５ ) ４ B － or C ３ F ７ COO － It should be noted that there are some unclear parts in the original text, marked with "?" above, which may need further clarification for a more accurate translation.is.

8. 2. The thermosetting resin composition according to claim 1, wherein the thermal initiator is contained in an amount of 0.1 to 1.0 wt % relative to 100 wt % of the total thermosetting resin composition.

9. The thermosetting resin composition according to claim 1 , wherein the heat curing agent comprises an amine-based curing agent.

10. The thermosetting resin composition according to claim 9 , wherein the heat curing agent comprises a compound represented by the following chemical formula 6: 【Chemistry 4】 In the above formula, R １０ ~R １３ are each independently hydrogen, C １ -C ４ alkyl group of C １ -C ４ an alkoxy group of C ２ -C ４ is an alkoxyalkyl group or a thiol group of the formula R １４ and R １５ are each independently hydrogen, C １ -C ４ is an alkyl group or an aryl group of the formula:

11. 2. The thermosetting resin composition according to claim 1, wherein the thermosetting agent is contained in an amount of 0.2 to 2.0% by weight based on 100% by weight of the total thermosetting resin composition.

12. A cured film comprising the thermosetting resin composition according to any one of claims 1 to 11.

13. The cured film according to claim 12, which is an overcoat film, a microlens, or a combined microlens and overcoat film.

14. A solid-state imaging device comprising the cured film according to claim 12.

Images