Sulfonic acid derivatives of naphthalimides and photoacid generators and photoresist compositions comprising the same

Abstract

The present invention relates to a sulfonic acid derivative of naphthalimide and a photo-acid generator and photoresist composition each containing the sulfonic acid derivative of naphthalimide, more specifically, to a sulfonic acid derivative of naphthalimide compound and a photo-acid generator and photoresist composition each containing the sulfonic acid derivative of naphthalimide compound, wherein the sulfonic acid derivative of naphthalimide compound has excellent absorbency to light of i-line (365 nm) wavelength, is very easy to prepare a polymerizable composition due to having very high solubility in an organic solvent, and has excellent thermal stability, and exhibits a good acid yield.

Description

Technical Field

[0001] This invention relates to a sulfonic acid derivative of naphthalimide and a photoacid-generating agent and photoresist composition comprising the sulfonic acid derivative of naphthalimide. More specifically, it relates to a sulfonic acid derivative compound of naphthalimide and a photoacid-generating agent and photoresist composition comprising the sulfonic acid derivative compound of naphthalimide, wherein the sulfonic acid derivative compound of naphthalimide has excellent absorption capacity for i-line (365nm) wavelength light, very high solubility in organic solvents, is very easy to prepare polymerizable compositions, has excellent thermal stability, and exhibits good acid production rate. Background Technology

[0002] Photoacid generators are compounds that produce acid when exposed to light. The acid generated by the photoacid generator decomposes a portion of the photoresist composition or causes cross-linking, depending on the composition of the photoresist, thereby changing the polarity of the polymer within the composition. This change in polymer polarity results in a difference in the solubility of the developer between the exposed and unexposed areas, which can achieve positive or negative photolithography.

[0003] In photoresist compositions, photoacid generators must have excellent energy sensitivity to irradiated light to form fine patterns. However, when using conventional photoacid generators, there is a problem that the sensitivity of the photoresist cannot be increased to a satisfactory level.

[0004] Therefore, there is a need to develop a photoacid generator that possesses excellent photosensitivity, enabling sufficient sensitivity to be achieved with minimal input, thus reducing costs. Furthermore, its excellent sensitivity allows for lower exposure doses and increased yield. In addition, improving the solubility of the photoacid generator in the main solvent of photoresist offers the advantage of readily preparing various compositions.

[0005] Various developments have been undertaken to improve the photosensitivity and solubility of naphthalenedicarboximide compounds. For example, Korean Patent Publication No. 10-2017-0125980 describes the preparation of naphthalenedicarboximide compounds using ultra-low temperature conditions of -70°C and metal compounds such as 1-butyllithium. Furthermore, Korean Patent Publication Nos. 10-2017-0042726 and 10-2012-0114353 describe the preparation of naphthalenedicarboximide compounds using bromine-substituted compounds. Summary of the Invention

[0006] Technical problems to be solved

[0007] The object of the present invention is to provide a sulfonic acid derivative compound of naphthalimide, a photoacid generator comprising the compound, and a photoresist composition, wherein the sulfonic acid derivative compound of naphthalimide exhibits excellent photosensitivity, high solubility in organic solvents, excellent thermal stability, and good acid generation rate suitable for use as a photoacid generator in photolithography.

[0008] Technical solution

[0009] To achieve the above objectives, a first aspect of the present invention provides a sulfonic acid derivative compound of naphthalenedicarbamate represented by the following chemical formula I:

[0010] [Chemical Formula I]

[0011]

[0012] In the chemical formula I,

[0013] R1 and R2 are each independently a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkylaryl group.

[0014] R3 can be independently a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, or of the formula R4-O-(CH2). n - groups, where n is an integer from 1 to 12, and R4 is a substituted or unsubstituted aliphatic hydrocarbon group.

[0015] A second aspect of the present invention provides a photoacid-generating agent comprising a sulfonic acid derivative compound of naphthalimide according to the present invention.

[0016] A third aspect of the present invention provides a photoresist composition comprising: a sulfonic acid derivative compound of naphthalenedicarboximide according to the present invention; and an adhesive resin.

[0017] According to another aspect of the present invention, a substrate coated with a photoresist composition according to the present invention is provided; a patterned substrate obtained by exposing and developing the coated substrate; a display device including the patterned substrate; and a semiconductor device comprising the patterned substrate.

[0018] Beneficial effects

[0019] The sulfonic acid derivative compound of naphthalimide according to the present invention has excellent solubility in photoresist solvents and excellent thermal stability, and is highly sensitive to photolithography light (e.g., i-line (365 nm) wavelength light). Therefore, when used as a photoacid generator component in a photoresist composition, even a small amount can provide a pattern with excellent developability, cone angle, pattern stability, etc., and can minimize degassing caused by the photoacid generator during exposure and post-baking processes, thus reducing contamination and having the advantage of minimizing defects that may result therefrom. Detailed Implementation

[0020] The present invention will now be described in detail.

[0021] The sulfonic acid derivative compound of naphthalimide of the present invention is represented by the following chemical formula I:

[0022] [Chemical Formula I]

[0023]

[0024] In the chemical formula I,

[0025] R1 and R2 are each independently a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkylaryl group.

[0026] R3 can be independently a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, or of the formula R4-O-(CH2). n - groups, where n is an integer from 1 to 12, and R4 is a substituted or unsubstituted aliphatic hydrocarbon group.

[0027] More specifically, in the chemical formula I,

[0028] R1 and R2 can each be independently substituted or unsubstituted C1-C. 12 Straight-chain alkyl or C3-C 12 Branched alkyl groups; substituted or unsubstituted C3-C 12 Alicyclic hydrocarbon group; substituted or unsubstituted C6-C 20 Aryl; substituted or unsubstituted C7-C 20 Aryl alkyl; or substituted or unsubstituted C7-C 20 Alkyl aryl,

[0029] R3 can be substituted or unsubstituted C1-C. 12 Straight-chain alkyl or C3-C 12 Branched alkyl groups; substituted or unsubstituted C3-C 12Alicyclic hydrocarbon group; substituted or unsubstituted C6-C 20 Aryl; substituted or unsubstituted C7-C 20 Arane; substituted or unsubstituted C7-C 20 Alkyl aryl; or substituted or unsubstituted C1-C 12 Alkoxy-C1-C 12 alkyl.

[0030] More specifically, in the chemical formula I,

[0031] R1 and R2 can each independently be a C1-C group substituted or unsubstituted with one or more halogen atoms or alicyclic hydrocarbon groups. 12 Straight-chain alkyl or C3-C 12 Branched alkyl groups; C3-C atoms substituted or unsubstituted with one or more halogen atoms. 12 Alicyclic hydrocarbon group; C6-C group substituted or unsubstituted with one or more halogen atoms. 20 Aryl group; surrounded by one or more halogen atoms or C1-C 12 alkylthio-substituted or unsubstituted C7-C 20 Aryl alkyl group; or C7-C atoms substituted or unsubstituted with one or more halogen atoms. 20 Alkyl aryl,

[0032] R3 can be a C1-C group that is substituted or unsubstituted with one or more halogen atoms or alicyclic hydrocarbon groups. 12 Straight-chain alkyl or C3-C 12 Branched alkyl groups; C3-C atoms substituted or unsubstituted with one or more halogen atoms. 12 Alicyclic hydrocarbon group; C6-C group substituted or unsubstituted with one or more halogen atoms. 20 Aryl group; surrounded by one or more halogen atoms or C1-C 12 alkylthio-substituted or unsubstituted C7-C 20 Aryl alkyl group; C7-C atoms substituted or unsubstituted with one or more halogen atoms. 20 Alkyl aryl; or C1-C substituted or unsubstituted with one or more halogen atoms. 12 Alkoxy-C1-C4 alkyl.

[0033] More specifically, in the chemical formula I,

[0034] R1 can be methyl, ethyl, trifluoromethyl, 2,2,2-trifluoroethyl, nonafluorobutyl, or toluenesulfonyl.

[0035] R2 can be methyl, ethyl, propyl, isopropyl, butyl, or cyclohexyl.

[0036] R3 can be methyl, ethyl, propyl, hexyl, heptyl, cyclohexyl, methoxyethyl, or butoxyethyl.

[0037] The substituents comprising the "alkyl" moiety described in this invention include all straight-chain or branched forms, and "cycloalkyl" includes not only monocyclic hydrocarbons but also polycyclic hydrocarbons. The "aryl" moiety described in this invention is an organic group derived from an aromatic hydrocarbon by removing a hydrogen atom, and includes monocyclic or fused-ring systems where each ring suitably contains 4-7 ring atoms, preferably 5 or 6 ring atoms, and includes multiple aryl groups linked by single bonds. Furthermore, the C1-C... 12 Alkyl groups can be more specifically C1-C 10 Alkyl groups, more specifically C1-C6 alkyl groups, C6-C 20 More specifically, aryl can be C6-C 18 Aryl, C3-C 12 More specifically, cycloalkyl groups can be C3-C 10 Cycloalkyl.

[0038] In one specific embodiment, the sulfonic acid derivative compound of the naphthalene dicarboximide of the present invention may be selected from the following compounds, but is not particularly limited thereto.

[0039]

[0040] In one specific embodiment, the sulfonic acid derivative compound of naphthalimide represented by the chemical formula I according to the present invention can be prepared via the route shown in the following reaction formula 1, but is not limited thereto.

[0041] [Reaction Formula 1]

[0042]

[0043] [In reaction formula 1, R1 to R3 are defined as in the preceding chemical formula I.]

[0044] The sulfonic acid derivative compound of naphthalimide of the present invention has excellent solubility in solvents for photoresists, excellent thermal stability, and excellent sensitivity to light for photolithography, and is therefore very useful as a photoacid-generating agent component in photoresist compositions.

[0045] Therefore, according to another aspect of the present invention, a photoacid generator and a photoresist composition comprising a sulfonic acid derivative compound of naphthalimide according to the present invention are provided.

[0046] The photoresist composition of the present invention comprises a sulfonic acid derivative compound of naphthalimide according to the present invention and an adhesive resin, wherein the sulfonic acid derivative compound of naphthalimide is included in the photoresist composition as a component for photo-induced acid production.

[0047] In one specific embodiment, the adhesive resin may be, for example, selected from polymers of hydroxystyrene or its derivatives; polymers of acrylic acid or its derivatives; polymers of methacrylic acid or its derivatives; copolymers of two or more monomers selected from hydroxystyrene, acrylic acid, methacrylic acid, and their derivatives; copolymers of two or more monomers selected from hydroxystyrene, styrene, and their derivatives; copolymers of three or more monomers selected from cycloolefins, maleic anhydride, acrylic acid, and their derivatives; copolymers of three or more monomers selected from cycloolefins, maleimide, acrylic acid, and their derivatives; polynorbornene; ring-opening translocation polymers; and polymers in which said polymers are partially substituted with acid-indestructible groups having alkali-soluble control capabilities; and combinations thereof, but are not particularly limited thereto. Examples of acid-indestructible groups incorporated into said polymers may include tertiary alkyl, trialkylsilyl, oxoalkyl, aryl-substituted alkyl, tetrahydropyran-2-yl and other heterocyclic groups, tertiary alkylcarbonyl, tertiary alkylcarbonylalkyl, alkoxycarbonyl, etc.

[0048] In one specific embodiment, the adhesive resin may be selected, for example, from polymers of hydroxystyrene or its derivatives; polymers of acrylic acid or its derivatives; polymers of methacrylic acid or its derivatives; copolymers of two or more monomers selected from hydroxystyrene, acrylic acid, methacrylic acid and their derivatives; copolymers of two or more monomers selected from hydroxystyrene, styrene and their derivatives; copolymers of three or more monomers selected from hydroxystyrene, styrene, acrylic acid, olefins, cycloolefins, maleic anhydride and their derivatives; and combinations thereof, but is not particularly limited thereto.

[0049] In one specific embodiment, the "derivative" may be, for example, the original compound surrounded by an alkyl or alkoxy group (more specifically C1-C2). 10 Alkyl or alkoxy) substitution, or when the original compound is an acid compound, it can be an alkyl group (more specifically C1-C) of the original compound. 10 Alkyl esters, but not specifically limited to them.

[0050] In one specific embodiment, the adhesive resin may, for example, be a copolymer of two or more monomers selected from the following monomers:

[0051] Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, acrylic acid Methacrylic acid, itaconic acid, maleic acid, maleic anhydride, monoalkyl maleate, monoalkyl itaconic acid, monoalkyl fumarate, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl(meth)acrylate, 2,3-epoxycyclohexyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 3-methyloxetane-3-methyl(meth)acrylate, 3-ethyloxetane-3-methyl(meth)acrylate, etc., and styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth)acrylamide, N-methyl(meth)acrylamide.

[0052] In one specific embodiment, the adhesive resin may be a polymer having unsaturated acrylic acid bonds on its side chains, for example, a copolymer obtained by adding an addition reaction between a carboxylic acid-containing copolymer and an epoxy compound.

[0053] More specifically, the copolymer containing carboxylic acids can be synthesized by reacting monomers containing carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and monoalkyl maleate, with alkyl methacrylates such as methyl methacrylate and hexyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, styrene, α-methylstyrene, acetoxystyrene, and N-methylmaleic acid. The copolymer is obtained by copolymerizing one or more monomers such as imide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth)acrylamide, and N-methyl(meth)acrylamide. The copolymer obtained by adding an addition reaction of such a carboxylic acid-containing copolymer with epoxy compounds such as glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl(meth)acrylate, 2,3-epoxycyclohexyl(meth)acrylate, and 3,4-epoxycyclohexylmethyl(meth)acrylate at a temperature of 40-180°C can be used as an adhesive resin.

[0054] In one specific embodiment, the weight-average molecular weight of the adhesive resin may be from 2,000 to 300,000, more specifically from 4,000 to 100,000, and the dispersion of the adhesive resin may be from 1 to 10, but is not particularly limited thereto.

[0055] In one specific embodiment, in 100% by weight of the photoresist composition of the present invention, in order to improve developability and minimize exposure dose, the content of the sulfonic acid derivative compound of the naphthalimide used as a photoacid generator can be 0.01-10% by weight, 0.01-9% by weight, 0.01-8% by weight, 0.01-7% by weight, 0.01-6% by weight, 0.01-5% by weight, 0.01-4% by weight, 0.01-3% by weight, 0.01-2% by weight, 0.01-1% by weight, 0.01-0.5% by weight, 0.01-0.4% by weight, 0.01-0.35% by weight, 0.01-0.3% by weight, 0.01-0.2% by weight, 0.05-10% by weight, etc. wt%, 0.05-9 wt%, 0.05-8 wt%, 0.05-7 wt%, 0.05-6 wt%, 0.05-5 wt%, 0.05-4 wt%, 0.05-3 wt%, 0.05-2 wt%, 0.05-1 wt%, 0.05-0.5 wt%, 0.05-0.4 wt%, 0.05-0.35 wt%, 0.05-0.3 wt%, 0.05-0.2 wt%, 0.1-10 wt%, 0.1-9 wt%, 0.1-8 wt%, 0.1-7 wt%, 0.1-6 wt%, 0.1-5 wt%, 0.1-4 wt%, 0.1-3 wt%, 0.1-2 wt%, 0.1-1 wt%, 0.1 -0.5 wt%, 0.1-0.4 wt%, 0.1-0.35 wt%, 0.1-0.3 wt%, 0.1-0.2 wt%, 0.2-10 wt%, 0.2-9 wt%, 0.2-8 wt%, 0.2-7 wt%, 0.2-6 wt%, 0.2-5 wt%, 0.2-4 wt%, 0.2-3 wt%, 0.2-2 wt%, 0.2-1 wt%, 0.2-0.5 wt%, 0.2-0.4 wt%, 0.2-0.35 wt%, 0.2-0.3 wt%, 0.25-10 wt%, 0.25-9 wt%, 0.25-8 wt%, 0.25-7 wt%, 0.25-6 wt%, 0.25-5 wt% %, 0.25-4 wt%, 0.25-3 wt%, 0.25-2 wt%, 0.25-1 wt%, 0.25-0.5 wt%, 0.25-0.4 wt%, 0.25-0.35 wt%, 0.25-0.3 wt%, 0.3-10 wt%, 0.3-9 wt%, 0.3-8 wt%, 0.3-7 wt%, 0.3-6 wt%, 0.3-5 wt%, 0.3-4 wt%, 0.3-3 wt%, 0.3-2 wt%, 0.3-1 wt%, 0.3-0.5 wt%, 0.3-0.4 wt%, 0.3-0.35 wt%, 0.35-10 wt%, 0.35-9 wt%, 0.35-8 wt%, 0.35-7 wt%, 0.35-6 wt%, 0.35-5 wt%, 0.35-4 wt%, 0.35-3 wt%, 0.35-2 wt%, 0.35-1 wt%, 0.35-0.5 wt%, 0.35-0.4 wt%, 0.4-10 wt%, 0.4-9 wt%, 0.4-8 wt%, 0.4-7 wt%, 0.4-6 wt%, 0.4-5 wt%, 0.4-4 wt%, 0.4-3 wt%, 0.4-2 wt%, 0.4-1 wt%, 0.4-0.5 wt%, more specifically, the content can be 0.1-5 wt%, but is not particularly limited thereto.

[0056] In one specific embodiment, in 100% by weight of the photoresist composition of the present invention, the content of the binder resin can be, for example, 30-99% by weight, 35-99% by weight, 40-99% by weight, 45-99% by weight, 50-99% by weight, 30-97% by weight, 35-97% by weight, 40-97% by weight, 45-97% by weight, 50-97% by weight, 30-95% by weight, etc., in order to adjust the patterning characteristics and impart film properties. wt%, 35-95 wt%, 40-95 wt%, 45-95 wt%, 50-95 wt%, 30-93 wt%, 35-93 wt%, 40-93 wt%, 45-93 wt%, 50-93 wt%, 30-90 wt%, 35-90 wt%, 40-90 wt%, 45-90 wt%, 50-90 wt%, 30-85 wt%, 35-85 wt%, 40-85 wt%, 4 5-85 wt%, 50-85 wt%, 30-80 wt%, 35-80 wt%, 40-80 wt%, 45-80 wt%, 50-80 wt%, 30-75 wt%, 35-75 wt%, 40-75 wt%, 45-75 wt%, 50-75 wt%, 30-70 wt%, 35-70 wt%, 40-70 wt%, 45-70 wt%, 50-70 wt%, 30-65 wt% The content can be 50-65% by weight, 35-65% by weight, 40-65% by weight, 45-65% by weight, 50-65% by weight, 30-60% by weight, 35-60% by weight, 40-60% by weight, 45-60% by weight, 50-60% by weight, 30-55% by weight, 35-55% by weight, 40-55% by weight, 45-55% by weight, 50-55% by weight, and more specifically, the content can be 50-99% by weight, but is not particularly limited to this.

[0057] The photoresist composition of the present invention may further contain a solvent.

[0058] As solvents, considering compatibility with adhesive resins, photoacid generators, and other compounds, the following solvents may be used alone or in combination of two or more: ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, methyl methoxypropionate, ethyl ethoxypropionate (EEP), ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol ethyl ether... Methyl acetate, ethyl diethylene glycol, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether (Diglyme), tetrahydrofuran (THF), methanol, ethanol, propanol, isopropanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, octane, etc.

[0059] In one specific embodiment, in 100% by weight of the photoresist composition of the present invention, in order to adjust the viscosity of the composition to the range of 1-50 centipoise seconds (cps), the content of the solvent may be, for example, 0.9-60% by weight, but is not particularly limited thereto.

[0060] As needed, the photoresist composition of the present invention may further include compatible additives such as defoamers and leveling agents.

[0061] According to another aspect of the present invention, a substrate coated with a photoresist composition according to the present invention is provided; a patterned substrate obtained by exposing and developing the coated substrate; a display device including the patterned substrate; and a semiconductor device comprising the patterned substrate.

[0062] In one specific embodiment, the substrate may be, for example, a silicon wafer substrate, the coating of the photoresist composition may be performed by known methods such as spin coating, the exposure may be performed by using light of an i-line (365 nm) wavelength, and the development may be performed by an alkaline developer such as an aqueous solution of trimethylammonium hydroxide (TMAH), but is not limited thereto.

[0063] The present invention will now be described in more detail through examples. However, the scope of the present invention is not limited thereto.

[0064] [Example]

[0065] Example 1: Preparation of 4-(1-ethoxybutyl)-naphthalimide trifluoromethanesulfonate (1)

[0066] Synthesis of 1,5-butyrylacenaphthene

[0067] 21.43 g (139.0 mmol) of acenaphthene was added to dichloromethane and cooled to below 10 °C. 19.46 g (145.9 mmol) of aluminum chloride was added and stirred for 30 minutes, followed by the slow addition of 14.81 g (139.0 mmol) of butyryl chloride. The reaction mixture was stirred at below 5 °C for 1 hour. Next, distilled water was added to the reaction product and stirred for 30 minutes, then the organic layer was separated. The separated organic layer was washed twice with distilled water, and the recovered organic layer was dried over anhydrous magnesium sulfate, with the solvent removed by vacuum distillation. The concentrated residue was purified by silica gel column chromatography (eluent: ethyl acetate: n-heptane = 1:4) to obtain 21.90 g (70.26%) of 5-butyrylacenaphthene.

[0068] 1 H NMR (δ) ppm ; CDCl3): δ8.65-8.62(dd,1H),8.05-8.02(d,1H),7.66-7.55(dd,1H),7.41-7.35(d,1 H),7.31-7.29(dd,1H),3.43-3.38(m,4H),3.05(t,2H),1.87-1.77(m,2H),1.04(t,3H)

[0069] MS(m / z): 224

[0070] Synthesis of 2,5-(1-ethoxybutyl)acenaphthene

[0071] 10.60 g (47.3 mmol) of 5-butyrylacenaphthene was dissolved in ethanol, and sodium borohydride was added. The mixture was stirred at 60 °C, then cooled to below 10 °C, and 19.17 mL of 10% hydrochloric acid aqueous solution was slowly added while stirring at 60 °C. When the reaction was terminated, distilled water was added to the reaction product and the mixture was stirred for 30 minutes. Next, ethyl acetate was added and stirred to separate the organic layer. The separated organic layer was washed with saturated sodium bicarbonate aqueous solution and distilled water, respectively. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed by vacuum distillation. The product obtained by vacuum distillation of the organic layer was purified by silica gel column chromatography (eluent: ethyl acetate: n-heptane = 1:10) to obtain 9.54 g (79.3%) of 5-(1-ethoxybutyl)acenaphthene.

[0072] 1 H NMR (δ) ppm; CDCl3): δ7.91(d,1H),7.45(dt,2H),7.31-7.25(m,2H),4.86(dd,1H),3.45-3.34(m,6H) ,1.95(m,1H),1.83(m,1H),1.56-1.45(m,1H),1.39-1.30(m,1H),1.20(t,3H),0.93(t,3H)

[0073] MS(m / z): 254

[0074] Synthesis of 3,4-(1-ethoxybutyl)naphthalenedicarboxylic anhydride

[0075] 7.24 g (28.4 mmol) of 5-(1-ethoxybutyl)acenaphthene was added to acetic acid, followed by 42.41 g (142.3 mmol) of sodium dichromate dihydrate. The mixture was stirred and refluxed at room temperature. After cooling to room temperature, the reaction mixture was poured into ice water, ethyl acetate was added, and the mixture was stirred for 30 minutes. The separated organic layer was washed with saturated sodium bicarbonate solution and distilled water, respectively. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed by vacuum distillation. The product obtained by vacuum distillation of the organic layer was purified by silica gel column chromatography (eluent: ethyl acetate: n-heptane = 1:10) to obtain 6.32 g (74.4%) of 4-(1-ethoxybutyl)naphthalenedicarboxylic anhydride.

[0076] 1 H NMR (δ) ppm ; CDCl3): δ8.73(dd,1H),8.65(dd,1H),8.62(d,1H),7.87(d,1H),7.83(dd,1H),5.00(d d,1H),3.46-3.38(m,2H),1.99-1.87(m,1H),1.84-1.73(m,1H),1.61-1.56(m,1H),1.54 -1.35(m,1H),1.23(t,3H),0.95(t,3H)

[0077] MS(m / z): 298

[0078] Reaction 4. Synthesis of N-hydroxy-4-(1-ethoxybutyl)naphthalenediamine

[0079] 4.60 g (15.4 mmol) of 4-(1-ethoxybutyl)naphthalenedicarboxylic anhydride, 1.61 g (23.1 mmol) of hydroxylamine hydrochloride, and 1.83 g (23.1 mmol) of pyridine were added to ethanol, and the mixture was heated to reflux. Ethanol was removed under reduced pressure to obtain 4.18 g of crude N-hydroxy-4-(1-ethoxybutyl)naphthalenedicarboxylic anhydride (crude product yield: 86.5%), which was then used in the next step of the reaction without further purification.

[0080] 1 H NMR (δ) ppm ; CDCl3): δ8.71-8.64(m,4H),7.86(d,1H),7.81(dd,1H),5.00(dd,1H),3.46-3.38(m,2H),2.02- 1.87(m,1H),1.85-1.73(m,1H),1.62-1.50(m,1H),1.46-1.36(m,1H),1.23(t,3H),0.95(t,3H).

[0081] MS(m / z): 313

[0082] Synthesis of reaction 5,4-(1-ethoxybutyl)naphthalimide trifluoromethanesulfonate (1)

[0083] 4.08 g (13.2 mmol) of N-hydroxy-4-(1-ethoxybutyl)naphthalenedicarboximide and 2.64 g (26.0 mmol) of triethylamine were added to dichloromethane, and the mixture was stirred for 30 minutes and cooled to below 5 °C. 2.19 g (13.2 mmol) of trifluoromethanesulfonyl chloride was added, and the mixture was stirred at room temperature. Next, distilled water was added to the reaction product, and the organic layer was separated by stirring. The separated organic layer was washed twice with distilled water, and the recovered organic layer was dried over anhydrous magnesium sulfate and the solvent was removed by vacuum distillation. The product obtained by vacuum distillation of the organic layer was purified by silica gel column chromatography (eluent: ethyl acetate: n-heptane = 1:4) to obtain 4.12 g (71.7%) of 4-(1-ethoxybutyl)naphthalenedicarboximide trifluoromethanesulfonate (1).

[0084] 1 H NMR (δ) ppm; CDCl3): δ8.76(dd,1H),8.71(dd,1H),8.68(d,1H),7.90(d,1H),7.85(dd,1H),5.01(dd,1H),3.49-3.35(m ,2H),1.97-1.88(m,1H),1.82-1.74(m,1H),1.62-1.51(m,1H),1.47-1.36(m,1H),1.23(t,3H),0.95(t,3H).

[0085] MS(m / z): 445

[0086] The following compounds were prepared using the same method as described in Example 1.

[0087]

[0088]

[0089] Preparation of adhesive resins

[0090] a) Preparation of adhesive resin 1

[0091] 200 ml of propylene glycol monomethyl ether acetate (PGMEA) and 1.5 g of azobisisobutyronitrile (AIBN) were added to a 500 ml polymerization container. Then, acetoxystyrene, styrene, and tert-butoxy methacrylate were added in a molar ratio of 50:25:25 to achieve a solid content of 40% by weight. The mixture was then stirred and polymerized at 70°C for 5 hours under a nitrogen atmosphere to prepare adhesive resin 1. The copolymer prepared as described above was confirmed to have a weight-average molecular weight of 25,000 and a dispersion of 2.0.

[0092] b) Preparation of adhesive resin 2

[0093] 200 ml of PGMEA and 1.5 g of AIBN were added to a 500 ml polymerization container. Then, acetoxystyrene, styrene, tert-butoxy methacrylate, and methyl methacrylate were added in a molar ratio of 40:25:25:10 to achieve a solid content of 40% by weight. The mixture was then stirred and polymerized at 70 °C for 5 hours under a nitrogen atmosphere to synthesize a copolymer. In the same reactor, 0.3 g of N,N-dimethylaniline and 20 molar amounts of glycidyl methacrylate were added, and the mixture was stirred at 100 °C for 10 hours to prepare adhesive resin 2, an acrylic polymer with unsaturated acrylic acid bonds on its side chains. The copolymer prepared as described above was confirmed to have a weight-average molecular weight of 20,000 and a dispersion of 2.1.

[0094] Measurement of solubility

[0095] The solubility of photoacid generators is crucial in the preparation of photoresist compositions. Therefore, the solubility of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexane, which are mainly used as solvents in photoresist compositions, was compared and measured with the solubility of compounds of Formula II below, and is shown in Table 1.

[0096] [Chemical Formula II]

[0097]

[0098] [Table 1] Solubility of photoacid-producing agents

[0099]

[0100] Measurement of thermal stability

[0101] When a photoacid-generating agent exhibits thermal stability during the photoresist preparation process, excellent stability can be expected. Therefore, a thermogravimetric analyzer was used to measure the temperature at which a 5% weight loss occurred and compared it with that of the compound of formula II.

[0102] [Table 2] Thermal stability of photoacid-producing agents

[0103] Compound numbering The temperature at which a 5% weight loss occurs (°C) 8 232 11 230 19 234 20 235 Chemical Formula II (Comparative Example) 223

[0104] Preparation of the photoresist composition in the examples

[0105] According to the components and contents listed in Table 3 below, binder resin 1 or binder resin 2, compound 8, compound 11, compound 19 or compound 20 as photoacid generators, and FC-430 (leveling agent from 3M, 0.02% by weight) are added sequentially to a reaction mixing tank equipped with an ultraviolet shielding film and a stirrer, and stirred at room temperature. Then, PGMEA as a solvent is added to make 100% by weight, thereby preparing a photoresist composition.

[0106] [Table 3] Preparation of photoresist compositions

[0107] Composition Number Adhesive resin (parts by weight) Photoacid-producing agent (parts by weight) Additives (parts by weight) 1 1(97) Compound 8 (0.4%) FC-430(0.1) 2 1(97) Compound 11 (0.4%) FC-430(0.1) 3 1(97) Compound 19 (0.4%) FC-430(0.1) 4 1(97) Compound 20 (0.4%) FC-430(0.1) 5 2(97) Compound 8 (0.4%) FC-430(0.1) 6 2(97) Compound 11 (0.4%) FC-430(0.1) 7 2(97) Compound 19 (0.4) FC-430(0.1) 8 2(97) Compound 20 (0.4%) FC-430(0.1) 9 1(60)+2(37) Compound 8 (0.4%) FC-430(0.1) 10 1(37)+2(60) Compound 8 (0.4%) FC-430(0.1)

[0108] Preparation of photoresist compositions for comparative examples

[0109] The photoresist composition was prepared by the same method as that used in the preparation of composition 3, except that a photoacid generator of chemical formula II was used instead of compound 19 as the photoacid generator.

[0110] [Chemical Formula II]

[0111]

[0112] Evaluation of photoresist compositions

[0113] The photoresist compositions of the embodiments and comparative examples were evaluated on a glass substrate. The pattern stability and cone angle of the photoresist compositions were measured, and the evaluation results are shown in Table 4 below.

[0114] 1) Pattern stability

[0115] Photoresist was spin-coated onto a silicon substrate and dried on a hot plate at 90°C for 1 minute. Exposure was then performed using a linewidth-pitch (10μm-10μm) step mask, followed by a post-exposure baking process and development in a 2.384% trimethylammonium hydroxide (TMAH) aqueous solution. The width of the pattern in the pitch area was measured after development.

[0116] 2) Cone angle

[0117] Photoresist was spin-coated onto a silicon substrate and dried on a hot plate at 90°C for 1 minute. Exposure was then performed using a linewidth-pitch (10μm-10μm) step mask, followed by a post-exposure baking process and development in a 2.384% TMAH aqueous solution. After development, the cone angle of the pitched portion was measured. A cone angle of 85° to 90° was considered good, while a cone angle less than 85° or greater than 91° was considered defective.

[0118] [Table 4]

[0119] Composition Number Size of the CD pattern spacing (μm) Relative to the value of the comparison example Cone angle state 1 12.3 1.06 good 2 12.1 1.04 good 3 12.2 1.05 good 4 12.1 1.04 good 5 12.0 1.03 good 6 12.2 1.05 good 7 12.1 1.04 good 8 12.0 1.03 good 9 12.2 1.05 good 10 12.0 1.03 good Comparative example 11.6 1.00 bad

Claims

1. A sulfonic acid derivative compound of naphthalenedicarbamate represented by the following chemical formula I: [Chemical Formula I] ， In the chemical formula I, R1 and R2 are each independently a C1-C group substituted or unsubstituted with one or more halogen atoms or alicyclic hydrocarbon groups. 12 Straight-chain alkyl or C3-C 12 Branched alkyl groups; C3-C atoms substituted or unsubstituted with one or more halogen atoms. 12 Alicyclic hydrocarbon group; C6-C group substituted or unsubstituted with one or more halogen atoms. 20 Aryl group; surrounded by one or more halogen atoms or C1-C 12 alkylthio-substituted or unsubstituted C7-C 20 Aryl alkyl group; or C7-C atoms substituted or unsubstituted with one or more halogen atoms. 20 alkylaryl, where R3 is a C1-C group substituted or unsubstituted with one or more halogen atoms or alicyclic hydrocarbon groups. 12 Straight-chain alkyl groups or C1-C atoms substituted or unsubstituted with one or more halogen atoms. 12 Alkoxy-C1-C4 alkyl.

2. The sulfonic acid derivative compound of naphthalenedicarbamate according to claim 1, wherein, R1 is methyl, ethyl, trifluoromethyl, 2,2,2-trifluoroethyl or nonafluorobutyl, R2 is methyl, ethyl, propyl, isopropyl, butyl or cyclohexyl, and R3 is methyl, ethyl, propyl, hexyl, heptyl, cyclohexyl, methoxyethyl or butoxyethyl.

3. The sulfonic acid derivative compound of naphthalenedicarbamate according to claim 1, wherein, The sulfonic acid derivative compound of the naphthalenedicarbamate is selected from the following compounds: 。 4. A photoacid-generating agent comprising a sulfonic acid derivative compound of naphthalenedicarbamate according to any one of claims 1 to 3.

5. A photoresist composition comprising: a sulfonic acid derivative compound of naphthalenedicarboximide according to any one of claims 1 to 3; and an adhesive resin.

6. A substrate coated with the photoresist composition according to claim 5.

7. A patterned substrate obtained by exposing and developing the coated substrate of claim 6.

8. A display device comprising a patterned substrate according to claim 7.

9. A semiconductor device comprising a patterned substrate according to claim 7.

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