Novel naphthalimide sulfonic acid ester derivatives, photoacid generators comprising the same, and photoresist compositions

Abstract

The present application relates to a naphthalimide sulfonic acid ester derivative and a photo-acid generator and photoresist composition comprising the same, and more particularly to a naphthalimide sulfonic acid ester derivative compound having excellent absorbance of light of i-line (365 nm) wavelength, high solubility in an organic solvent, and excellent thermal stability, and exhibiting a good acid yield, and a photo-acid generator and photoresist composition comprising the same.

Description

TECHNICAL FIELD

[0001] The present application relates to a naphthalimide sulfonic acid ester derivative and a photo-acid generator and a photoresist composition comprising the same, and more particularly, to a naphthalimide sulfonic acid ester derivative compound having excellent absorbance of light of i-line (365 nm) wavelength, high solubility in an organic solvent, and excellent thermal stability, and exhibiting a good acid yield, and a photo-acid generator and a photoresist composition comprising the same. BACKGROUND

[0002] A photo-acid generator is a compound that generates an acid by light irradiation, and depending on the composition of a photoresist composition, the acid generated from the photo-acid generator decomposes a part of the composition or causes crosslinking, thereby changing the polarity of a polymer within the composition. This change in the polarity of the polymer causes a difference in solubility to a developer between an exposed portion and an unexposed portion, as a result of which positive or negative photoresist can be achieved.

[0003] In a photoresist composition, a photo-acid generator has excellent energy sensitivity to irradiated light in order to form a fine pattern, but there is a problem that the sensitivity of a photoresist cannot be increased to a satisfactory level using only a conventional photo-acid generator.

[0004] Accordingly, there is a need to develop a photo-acid generator that has excellent light sensitivity and can achieve sufficient sensitivity with a small amount, thus having the effect of reducing costs, and has excellent sensitivity, thus can reduce the amount of exposure, and can improve yield. In addition, increasing the solubility of the photo-acid generator in the main solvent of a photoresist has the advantage that various compositions can be easily prepared.

[0005] In order to improve light sensitivity and improve solubility, various developments have been made on naphthalimide compounds. For example, Korean Patent Publication No. 10-2017-0125980 prepared a naphthalimide compound by using an ultralow temperature condition of -70°C and a metal compound such as 1-butyl lithium, and Korean Patent Publication No. 10-2017-0042726 and Korean Patent Publication No. 10-2012-0114353 prepared a naphthalimide compound by using a compound substituted with bromine. SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] The present invention relates to a naphthalimide sulfonic acid ester derivative compound having excellent absorbance of i-line (365 nm) wavelength light, high solubility in an organic solvent, and excellent thermal stability, and exhibiting a good acid yield, a photoacid generator comprising the same, and a photoresist composition comprising the same.

[0008] Technical Solution

[0009] To achieve the above object, a first aspect of the present invention provides a naphthalimide sulfonic acid ester derivative compound represented by the following Chemical Formula I or Chemical Formula II:

[0010] [Chemical Formula I]

[0011]

[0012] In the Chemical Formula I, R1 is a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, or a substituted or unsubstituted alkylaryl group; R2 is a hydrogen atom or a tert-butyl group; m is an integer of 1 to 4; and n is an integer of 0 to 2.

[0013] [Chemical Formula II]

[0014]

[0015] In the Chemical Formula II, R1, m, and n are the same as defined in the Chemical Formula I, and R2 is a hydrogen atom.

[0016] A second aspect of the present invention provides a photoacid generator comprising the naphthalimide sulfonic acid ester derivative compound of the present invention.

[0017] A third aspect of the present invention provides a photoresist composition comprising the naphthalimide sulfonic acid ester derivative compound of the present invention and a binder resin.

[0018] A fourth aspect of the present invention provides an acenaphthene derivative compound represented by the following Chemical Formula III or Chemical Formula IV:

[0019] [Chemical Formula III]

[0020]

[0021] In the Chemical Formula III, R2 is a hydrogen atom or a tert-butyl group; m is an integer of 1 to 4; and n is an integer of 0 to 2.

[0022] [Chemical Formula IV]

[0023]

[0024] In the chemical formula IV, R2 is a hydrogen atom; m and n are the same as defined in the chemical formula III.

[0025] A fifth aspect of the present application provides a method for preparing the acenaphthene derivative compound represented by the chemical formula III or the chemical formula IV, the method comprising the step of reducing the compound of the following chemical formula III' or chemical formula IV':

[0026] [Chemical Formula III']

[0027]

[0028] [Chemical Formula IV']

[0029]

[0030] In the chemical formula III' and the chemical formula IV', R2, m and n are the same as defined in the chemical formula III and the chemical formula IV, respectively.

[0031] Advantages

[0032] The naphthalimide sulfonic acid ester derivative compound of the present application has excellent solubility in a solvent for a photoresist, and has excellent thermal stability, and has very excellent sensitivity to a light for photoetching (for example, i-line (365 nm) wavelength light), and thus, when used as a photoacid generator component of a photoresist composition, even if used in a small amount, it can provide a pattern having excellent development, taper angle, pattern stability, etc., and can minimize outgassing due to the photoacid generator in an exposure and post-baking process, and thus, can reduce contamination, and has the advantage that defects that can be generated thereby can be minimized. DETAILED DESCRIPTION

[0033] Hereinafter, the present application will be described in detail.

[0034] The naphthalimide sulfonic acid ester derivative compound of the present application is represented by the following chemical formula I or chemical formula II:

[0035] [Chemical Formula I]

[0036]

[0037] In the chemical formula I, R1 is a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, or a substituted or unsubstituted alkylaryl group; R2 is a hydrogen atom or a tert-butyl group; m is an integer of 1 to 4; n is an integer of 0 to 2;

[0038] [Chemical Formula II]

[0039]

[0040] In the Chemical Formula II, R1, m and n are the same as defined in the Chemical Formula I, and R2 is a hydrogen atom.

[0041] More specifically, in the Chemical Formula I and the Chemical Formula II, R1may be a substituted or unsubstituted C1-C 12 linear alkyl group or a C3-C 12 branched alkyl group; a substituted or unsubstituted C3-C 12 alicyclic hydrocarbon group; a substituted or unsubstituted C6-C 20 aryl group; a substituted or unsubstituted C7-C 20 arylalkyl group; or a substituted or unsubstituted C7-C 20 alkylaryl group.

[0042] Further specifically, in the Chemical Formula I and the Chemical Formula II, R1may be a substituted or unsubstituted C1-C 12 linear alkyl group or a C3-C 12 branched alkyl group; a substituted or unsubstituted C3-C 12 alicyclic hydrocarbon group; a substituted or unsubstituted C6-C 20 aryl group; a substituted or unsubstituted C7-C 12 alkylthio group or a C7-C 20 arylalkyl group; or a substituted or unsubstituted C7-C 20 alkylaryl group.

[0043] Further specifically, the R1may be a methyl group, an ethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a nonafluorobutyl group or a tolyl group.

[0044] The substituent groups containing "alkyl" moieties described in the present application include all linear forms or branched forms, and "cycloalkyl" includes not only monocyclic hydrocarbons but also polycyclic hydrocarbons. The "aryl" described in the present application is an organic group derived from an aromatic hydrocarbon by removing one hydrogen, and includes a monocyclic ring or a fused ring system suitably containing 4 to 7 ring atoms, preferably 5 or 6 ring atoms in each ring, and includes a form in which a plurality of aryl groups are connected by a single bond. Furthermore, the C1-C 12 alkyl described in the present application can be more specifically a C1-C 10 alkyl, further specifically a C1-C6alkyl, a C6-C 20 aryl, more specifically a C6-C 18 aryl, a C3-C 12Cycloalkyl can be more specifically C3-C 10 Cycloalkyl.

[0045] In one embodiment, the naphthalene dicarboximide sulfonic acid ester derivative compound of the present application can be selected from the following compounds, but is not particularly limited thereto.

[0046]

[0047] The naphthalene dicarboximide sulfonic acid ester derivative compound of the present application has excellent solubility in a photoresist solvent, and has excellent thermal stability, and very excellent sensitivity to a light used for photoetching, and thus is very useful as a photoacid generator component of a photoresist composition.

[0048] Accordingly, according to another aspect of the present application, there is provided a photoacid generator and a photoresist composition comprising the naphthalene dicarboximide sulfonic acid ester derivative compound of the present application.

[0049] The photoresist composition of the present application comprises the naphthalene dicarboximide sulfonic acid ester derivative compound of the present application and a binder resin, wherein the naphthalene dicarboximide sulfonic acid ester derivative compound is contained in the photoresist composition as a photoacid generator component.

[0050] In one embodiment, the binder resin can be selected from, for example, a polymer of hydroxystyrene or a derivative thereof; a polymer of acrylic acid or a derivative thereof; a polymer of methacrylic acid or a derivative thereof; a copolymer of two or more monomers selected from the group consisting of hydroxystyrene, acrylic acid, methacrylic acid, and derivatives thereof; a copolymer of two or more monomers selected from the group consisting of hydroxystyrene, styrene, and derivatives thereof; a copolymer of three or more monomers selected from the group consisting of cycloalkene, maleic anhydride, acrylic acid, and derivatives thereof; a copolymer of three or more monomers selected from the group consisting of cycloalkene, maleimide, acrylic acid, and derivatives thereof; polynorbornene; metathesis ring-opening polymer; and a polymer in which the polymer is partially substituted with an acid-labile group having base-solubility control ability; and combinations thereof, but is not particularly limited thereto. Examples of the acid-labile group introduced into the polymer can include tertiary alkyl, trialkylsilyl, oxoalkyl, aryl-substituted alkyl, heteroalicyclic group such as tetrahydropyran-2-yl, tertiary alkylcarbonyl, tertiary alkylcarbonylalkyl, alkoxycarbonyl, and the like.

[0051] In one embodiment, the adhesive resin can be, for example, selected from the group consisting of a polymer of hydroxystyrene or a derivative thereof; a polymer of acrylic acid or a derivative thereof; a polymer of methacrylic acid or a derivative thereof; a copolymer of two or more monomers selected from the group consisting of hydroxystyrene, acrylic acid, methacrylic acid, and derivatives thereof; a copolymer of two or more monomers selected from the group consisting of hydroxystyrene, styrene, and derivatives thereof; a copolymer of three or more monomers selected from the group consisting of hydroxystyrene, styrene, acrylic acid, olefin, cyclic olefin, maleic anhydride, and derivatives thereof; and combinations thereof, but is not particularly limited thereto.

[0052] In one embodiment, the "derivative" can be, for example, a corresponding compound substituted with an alkyl or alkoxy group (more specifically, a C1-C20alkyl or alkoxy group), or when the corresponding compound is an acid compound, an alkyl (more specifically, a C1-C20alkyl) ester of the corresponding compound, but is not particularly limited thereto. 10 In one embodiment, the "derivative" can be, for example, a corresponding compound substituted with an alkyl or alkoxy group (more specifically, a C1-C20alkyl or alkoxy group), or when the corresponding compound is an acid compound, an alkyl (more specifically, a C1-C20alkyl) ester of the corresponding compound, but is not particularly limited thereto. 10 In one embodiment, the "derivative" can be, for example, a corresponding compound substituted with an alkyl or alkoxy group (more specifically, a C1-C20alkyl or alkoxy group), or when the corresponding compound is an acid compound, an alkyl (more specifically, a C1-C20alkyl) ester of the corresponding compound, but is not particularly limited thereto.

[0053] In one embodiment, the adhesive resin can be, for example, a copolymer of two or more monomers selected from the group consisting of:

[0054] methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, fumaric acid monoalkyl ester, 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, and the like, and styrene, α-methylstyrene, acetoxy styrene, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, (meth)acrylamide, N-methyl (meth)acrylamide.

[0055] In one embodiment, the adhesive resin can be a polymer having an acrylic unsaturated bond on a side chain, for example, can be a copolymer obtained by addition reaction of a copolymer containing a carboxylic acid with an epoxy compound.

[0056] More specifically, the copolymer containing a carboxylic acid can be obtained by copolymerization of one or more of acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester, and the like containing a carboxylic acid with (meth) methyl acrylate, (meth) methyl acrylate, (meth) acrylate, (meth) cyclohexyl acrylate, (meth) isobornyl acrylate, (meth) adamantyl acrylate, (meth) dicyclopentyl acrylate, (meth) dicyclopentenyl acrylate, (meth) benzyl acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, styrene, α-methyl styrene, acetoxy styrene, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, (meth) acrylamide, N-methyl (meth) acrylamide, and the like, and the copolymer obtained by addition reaction of such a copolymer containing a carboxylic acid with glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like at a temperature of 40 to 180°C can be used as the adhesive resin.

[0057] In one embodiment, the weight average molecular weight of the adhesive resin can be 2000 to 300000, more specifically 4000 to 100000, and the dispersity of the adhesive resin can be 1 to 10, but is not particularly limited thereto.

[0058] In one specific embodiment, in 100% by weight of the photoresist composition of the present application, the content of the naphthalene dicarboximide sulfonic acid ester derivative compound 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, 0.05-9% by weight, 0.05-8% by weight, 0.05-7% by weight, 0.05-6% by weight, 0.05-5% by weight, 0.05-4% by weight, 0.05-3% by weight, 0.05-2% by weight, 0.05-1% by weight, 0.05-0.5% by weight, 0.05-0.4% by weight, 0.05-0.35% by weight, 0.05-0.3% by weight, 0.05-0.2% by weight, 0.1-10% by weight, 0.1-9% by weight, 0.1-8% by weight, 0.1-7% by weight, 0.1-6% by weight, 0.1-5% by weight, 0.1-4% by weight, 0.1-3% by weight, 0.1-2% by weight, 0.1-1% by weight, 0.1-0.5% by weight, 0.1-0.4% by weight, 0.1-0.35% by weight, 0.1-0.3% by weight, 0.1-0.2% by weight, 0.2-10% by weight, 0.2-9% by weight, 0.2-8% by weight, 0.2-7% by weight, 0.2-6% by weight, 0.2-5% by weight, 0.2-4% by weight, 0.2-3% by weight, 0.2-2% by weight, 0.2-1% by weight, 0.2-0.5% by weight, 0.2-0.4% by weight, 0.2-0.35% by weight, 0.2-0.3% by weight, 0.25-10% by weight, 0.25-9% by weight, 0.25-8% by weight, 0.25-7% by weight, 0.25-6% by weight, 0.25-5% by weight, 0.25-4% by weight, 0.25-3% by weight, 0.25-2% by weight, 0.25-1% by weight, 0.25-0.5% by weight, 0.25-0.4% by weight, 0.25-0.35% by weight, 0.25-0.3% by weight, 0.3-10% by weight, 0.3-9% by weight, 0.3-8% by weight, 0.3-7% by weight, 0.3-6% by weight, 0.3-5% by weight, 0.3-4% by weight, 0.3-3% by weight, 0.3-2% by weight, 0.3-1% by weight, 0.3-0.5% by weight, 0.3-0.4% by weight, 0.3-0.35% by weight, 0.35-10% by weight, 0.35-9% by weight, 0.35-8% by weight, 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.

[0059] In one embodiment, the content of the binder resin can be, for example, 30-99 wt%, 35-99 wt%, 40-99 wt%, 45-99 wt%, 50-99 wt%, 30-97 wt%, 35-97 wt%, 40-97 wt%, 45-97 wt%, 50-97 wt%, 30-95 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%, 45-85 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%, 35-65 wt%, 40-65 wt%, 45-65 wt%, 50-65 wt%, 30-60 wt%, 35-60 wt%, 40-60 wt%, 45-60 wt%, 50-60 wt%, 30-55 wt%, 35-55 wt%, 40-55 wt%, 45-55 wt%, 50-55 wt%, more specifically, the content can be 50-99 wt%, but is not particularly limited thereto, in 100 wt% of the photoresist composition of the present application, in order to adjust the pattern properties and impart thin film physical properties.

[0060] The photoresist composition of the present application can further comprise a solvent.

[0061] As the solvent, in consideration of the compatibility with the binder resin, the photoacid generator, and other compounds, the following solvent can be used alone or two or more of the following solvents can be used in mixture: ethyl acetate, butyl acetate, diglyme, diethyl 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 methyl acetate, diethylene glycol ethyl acetate, 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, and the like.

[0062] In one specific embodiment, in order to adjust the viscosity of the composition to the range of 1 to 50 cps, the content of the solvent can be, for example, 0.9 to 60% by weight, in 100% by weight of the photoresist composition of the present application, but is not particularly limited thereto.

[0063] The photoresist composition of the present application can further include a defoaming agent, a leveling agent, and the like, as necessary, with compatible additives.

[0064] In one specific embodiment, the naphthalene dicarboximide sulfonic acid ester derivative compound represented by the Chemical Formula I can be prepared according to the following Reaction Formula 1, and the naphthalene dicarboximide sulfonic acid ester derivative compound represented by the Chemical Formula II can be prepared according to the following Reaction Formula 2.

[0065] [Reaction Formula 1]

[0066]

[0067] [Reaction Formula 2]

[0068]

[0069] [In the Reaction Formula 1 and Reaction Formula 2, R1, R2, m, and n are the same as defined in the Chemical Formula I and Chemical Formula II, respectively.]

[0070] Accordingly, according to another aspect of the present application, as an intermediate for preparing the naphthalene dicarboximide sulfonic acid ester derivative compound of the present application, there are provided acenaphthene derivative compounds represented by the following Chemical Formula III or Chemical Formula IV, and methods for preparing the same:

[0071] [Chemical Formula III]

[0072]

[0073] In the Chemical Formula III, R2 is a hydrogen atom or a tert-butyl group; m is an integer of 1 to 4; and n is an integer of 0 to 2.

[0074] [Chemical Formula IV]

[0075]

[0076] In the Chemical Formula IV, R2 is a hydrogen atom; and m and n are the same as defined in the Chemical Formula III.

[0077] The method for preparing the acenaphthene derivative compound represented by the Chemical Formula III or Chemical Formula IV according to the present application includes a step of reducing a compound of the following Chemical Formula III' or Chemical Formula IV', respectively:

[0078] [Chemical Formula III']

[0079]

[0080] [Chemical Formula IV']

[0081]

[0082] In the Chemical Formula III' and Chemical Formula IV', R2, m and n are the same as defined in the Chemical Formula III and Chemical Formula IV, respectively.

[0083] In one specific embodiment, the reducing step can be performed in the presence of a base, for example, in the presence of potassium hydroxide, sodium hydroxide, potassium tert-butoxide or a combination thereof, at a high temperature, for example, at a temperature of 100-180°C.

[0084] Hereinafter, the present application will be described in more detail by way of examples and comparative examples. However, the scope of the present application is not limited thereto.

[0085] [Examples]

[0086] Example 1: Preparation of 4-cyclopropanemethylnaphthalene dicarboxamide trifluoromethane sulfonate (1)

[0087] Reaction 1. Synthesis of 5-cyclopropanecarbonylacenaphthylene

[0088] To 5.0 g (32.4 mmol) of acenaphthene in dichloromethane was added 4.55 g (34.0 mmol) of aluminum chloride and stirred for 30 minutes, and then 3.39 g (32.4 mmol) of cyclopropanecarbonyl chloride diluted with dichloromethane was slowly added and the reaction was stirred for 1 hour at 5°C or less. Next, distilled water was added to the reaction product and stirred for 30 minutes, and then the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was refined by silica gel column chromatography (developing solvent: ethyl acetate : n-hexane = 1 : 4) to obtain 6.03 g (83.7%) of 5-cyclopropanecarbonylacenaphthene.

[0089] 1 H NMR (δ ppm ; CDC13): 1.08-1.02 (2H, m), 1.31-1.35 (2H, m), 2.63-2.74 (1H, m)), 3.40 (4H, m), 7.31-7.36 (2H, m), 7.51-7.56 (1H, dd), 8.10-8.12 (1H, d), 8.42-8.44 (1H, d)

[0090] MS (m / z): 222

[0091] Reaction 2. Synthesis of 5-cyclopropylmethylacenaphthylene

[0092] To 5.75 g (25.9 mmol) of 5-cyclopropanecarbonylacenaphthene, 3.50 g (38.8 mmol) of methyl carbazate and 4.66 g (77.6 mmol) of acetic acid in ethanol was heated to reflux. Next, the reaction was cooled to room temperature, and ethanol was removed by reduced pressure. Ethyl acetate and distilled water were added to the concentrated residue and stirred, and then the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was added to 7.27 g (129.5 mmol) of potassium hydroxide and triethylene glycol, warmed to 140°C and stirred, and then cooled to room temperature, n-hexane and distilled water were added and stirred, and then the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distillation under reduced pressure of the organic layer was refined by silica gel column chromatography (developing solvent: n-hexane alone) to obtain 4.24 g (65.4%) of solid 5-cyclopropylmethylacenaphthene.

[0093] 1 H NMR (δppm ; CDCl3):0.23-0.27(2H,m)0.52-0.56(2H,m),1.12-1.20(1H,m),2.93-2.94(2H,d)3.35-3.42(4H ,m),7.21-7.24(1H,d)7.27-7.28(1H,d),7.37-7.39(1H,d),7.44-7.47(1H,dd),7.71-7.73(1H,d)

[0094] MS(m / z): 208

[0095] Reaction 3. Synthesis of 4-cyclopropylmethyl naphthalene anhydride

[0096] 15.0 g (72.0 mmol) of 5-cyclopropylmethylacenaphthene was added to acetic acid, followed by 107.3 g (360.1 mmol) of sodium dichromate dihydrate. The mixture was stirred and heated to reflux at room temperature. The mixture was then cooled to room temperature, and the reaction mixture was poured into ice water. The resulting solid was filtered and washed successively with distilled water and ethanol. The obtained solid was dried to give 13.70 g (75.4%) of 4-cyclopropylmethylnaphthalic anhydride.

[0097] 1 H NMR (δ) ppm ; CDCl3):0.31-0.36(2H,m),0.64-0.70(2H,m),1.14-1.23(1H,m),3.14-3.16(2H ,d),7.82-7.86(2H,m),8.51-8.54(1H,dd),8.58-8.60(1H,d),8.63-8.65(1H,dd)

[0098] MS(m / z): 252

[0099] Reaction 4. Synthesis of N-hydroxy-4-cyclopropylmethyl naphthalene dicarboxamide

[0100] 13.40 g (53.1 mmol) of 4-cyclopropylmethylnaphthalic anhydride was added to ethanol, along with 5.54 g (79.7 mmol) of hydroxylamine hydrochloride and 6.30 g (79.7 mmol) of pyridine, and the mixture was heated to reflux. Ethanol was removed under reduced pressure to obtain 13.30 g of crude N-hydroxy-4-cyclopropylmethylnaphthalimide (crude product yield: 93.7%), which was then used in the next reaction without further purification.

[0101] 1 H NMR (δ) ppmH NMR (CDC13, 300 MHz): 0.31-0.35 (2H, m), 0.65-0.70 (2H, m), 1.12-1.21 (IH, m), 3.15-3.16 (2H, d), 7.83-7.87 (2H, m), 8.54-8.56 (IH, dd), 8.62-8.64 (IH, d), 8.67-8.69 (IH, dd)

[0102] MS (m / z): 267

[0103] Reaction 5. Synthesis of 4-cyclopropanemethyl naphthalene dicarboxamide trifluoromethanesulfonate (1)

[0104] To 13.75 g (51.4 mmol) of N-hydroxy-5-cyclopropylmethylnaphthalene dicarboxylic imide in dichloromethane was added 10.41 g (102.9 mmol) of triethylamine and stirred for 30 minutes and cooled to 5°C or less. 8.67 g (51.4 mmol) of trifluoromethanesulfonyl chloride was added and then stirred at normal temperature. Then, distilled water was added and after stirring, the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate and the solvent was removed by distillation under reduced pressure. The product obtained by distillation under reduced pressure of the organic layer was refined by silica gel column chromatography (developing agent: ethyl acetate:n-hexane = 1:4) to obtain 16.24 g (79.1%) of 4-cyclopropanemethylnaphthalene dicarboxylic imide trifluoromethanesulfonate (1).

[0105] 1 H NMR (CDC13, 300 MHz): 0.31-0.35 (2H, m), 0.65-0.70 (2H, m), 1.12-1.21 (IH, m), 3.15-3.16 (2H, d), 7.83-7.87 (2H, m), 8.54-8.56 (IH, dd), 8.62-8.64 (IH, d), 8.67-8.69 (IH, dd) ppm ; CDC13): 0.31-0.35 (2H, m), 0.65-0.70 (2H, m), 1.12-1.21 (IH, m), 3.15-3.16 (2H, d), 7.83-7.87 (2H, m), 8.54-8.56 (IH, dd), 8.62-8.64 (IH, d), 8.67-8.69 (IH, dd)

[0106] 1.13-1.21 (IH, m), 3.15-3.16 (2H, d), 7.83-7.87 (2H, m), 8.54-8.56 (IH, dd), 8.62-8.64 (IH, d), 8.67-8.69 (IH, dd)

[0107] MS (m / z): 399

[0108] The following compounds were prepared by the same method as in Example 1.

[0109]

[0110] Example 2: Preparation of 2,5-dicyclopropanemethylnaphthalene dicarboxylic imide trifluoromethanesulfonate (9)

[0111] Reaction 1. Synthesis of 3,6-cyclohexanecarbonylacenaphthylene

[0112] To 6.0 g (38.9 mmol) of acenaphthene in dichloromethane was added 10.89 g (81.7 mmol) of aluminum chloride and stirred for 30 minutes, and then 12.55 g (85.6 mmol) of chlorocyclohexane diluted with dichloromethane was slowly added and the reaction was stirred for 1 hour at 5°C or less. Then, distilled water was added to the reaction and stirred for 30 minutes, and then the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was refined by silica gel column chromatography (developing solvent: ethyl acetate : n-hexane = 1 : 4) to obtain 10.30 g (70.7%) of 3,6-dicyclohexylcarbonylacenaphthene.

[0113] 1 H NMR (δ ppm ; CDC13): 1.08-1.02 (2H, m), 1.31-1.35 (2H, m), 2.63-2.74 (1H, m)), 3.41-3.48 (2H, t), 3.78-3.85 (2H, t) 7.36-7.41 (2H, m), 8.13-8.15 (1H, d), 8.45-8.47 (1H, d)

[0114] MS (m / z): 290

[0115] Reaction 2. Synthesis of 3,6-dicyclohexylmethylacenaphthylene

[0116] To 10.75 g (28.0 mmol) of 3,6-dicyclohexylcarbonylacenaphthene, 7.58 g (84.1 mmol) of methyl hydrazinecarboxylate, and 10.10 g (168.2 mmol) of acetic acid in ethanol was heated to reflux. Next, the reaction was cooled to room temperature, and ethanol was removed by reduced pressure. Ethyl acetate and distilled water were added to the concentrated residue and stirred, and then the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was added to 15.71 g (280.0 mmol) of potassium hydroxide and triethylene glycol, and warmed to 140°C and stirred. Then, after cooling to room temperature, ethyl acetate and distilled water were added and stirred, and then the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distillation under reduced pressure of the organic layer was refined by silica gel column chromatography (developing solvent: ethyl acetate : n-hexane = 1 : 4) to obtain 4.27 g (58.2%) of 3,6-dicyclohexylmethylacenaphthene.

[0117] 1H NMR (δ ppm ; CDC13): 0.23-0.27 (4H, m) 0.52-0.56 (4H, m), 1.12-1.20 (2H, m), 2.87-2.88 (2H, d), 2.90-2.91 (2H, d) 3.35-3.42 (2H, t), 3.42-3.69 (2H, t), 7.25-7.29 (IH, d) 7.31-7.32 (IH, d), 7.47-7.50 (IH, d), 7.73-7.75 (IH, d)

[0118] MS (m / z): 262

[0119] Reaction 3. Synthesis of 2,5-dicyclopropylmethyl naphthalene anhydride

[0120] In acetic acid was added 2.35 g (6.8 mmol) of 3,6-dicyclohexylmethyl acenaphthene, followed by 10.10 g (33.9 mmol) of sodium dichromate dihydrate, and stirred at normal temperature and heated to reflux. Then, cooled to normal temperature, and then the reaction mixture was poured into ice water, and ethyl acetate was added and stirred, and then the organic layer was separated. The separated organic layer was washed with distilled water 2 times, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was refined by silica gel column chromatography (developing agent: ethyl acetate:n-hexane = 1:4), thereby obtaining 1.78 g (67.2%) of 2,5-dicyclopropylmethyl naphthalene anhydride.

[0121] 1 H NMR (δ ppm ; CDC13): 0.31-0.36 (4H, m) 0.64-0.70 (4H, m), 1.14-1.23 (2H, m), 3.14-3.16 (2H, d), 3.17-3.19 (2H, d), 7.82-7.86 (2H, m), 8.58-8.60 (IH, d), 8.63-8.65 (IH, d)

[0122] MS (m / z): 306

[0123] Reaction 4. Synthesis of N-hydroxy-2,5-dicyclopropylmethyl naphthalene dicarboxamide

[0124] To 5.24 g (13.4 mmol) of 2,5-dicyclopropylmethylnaphthalene anhydride in ethanol was added 1.40 g (20.1 mmol) of hydroxylamine hydrochloride and 1.59 g (20.1 mmol) of pyridine and heated to reflux. Ethanol was removed under reduced pressure and purified by silica gel column chromatography (developing solvent: ethyl acetate : n-hexane = 1 : 2) to obtain 3.54 g (65.1 %) of N-hydroxy-2,5-dicyclopropylmethylnaphthalene dicarboxamide.

[0125] 1 H NMR (δ ppm ; CDC13): 0.31-0.35 (4H, m), 0.65-0.70 (4H, m), 1.13-1.21 (2H, m), 3.15-3.16 (2H, d), 3.20-3.21 (2H, d), 7.83-7.87 (2H, d), 8.62-8.64 (1H, d), 8.67-8.69 (1H, d)

[0126] MS (m / z): 321

[0127] Reaction 5. Synthesis of 2,5-dicyclopropanemethyl naphthalene dicarboxamide trifluoromethanesulfonate (9)

[0128] To 4.08 g (10.1 mmol) of N-hydroxy-2,5-dicyclopropylmethylnaphthalene dicarboxamide in dichloromethane was added 2.04 g (20.1 mmol) of triethylamine and stirred for 30 minutes and cooled to below 5°C. 1.70 g (10.1 mmol) of trifluoromethanesulfonyl chloride was added and stirred at room temperature. Then, distilled water was added and after stirring, the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distillation under reduced pressure of the organic layer was purified by silica gel column chromatography (developing solvent: ethyl acetate : n-hexane = 1 : 4) to obtain 3.52 g (65.1 %) of 2,5-dicyclopropanemethylnaphthalene dicarboxamide trifluoromethanesulfonate (9).

[0129] 1 H NMR (δ ppm ; CDC13): 0.31-0.35 (4H, m), 0.65-0.70 (4H, m), 1.13-1.21 (2H, m), 3.15-3.16 (2H, d), 3.20-3.21 (2H, d), 7.83-7.87 (2H, d), 8.62-8.64 (1H, d), 8.67-8.69 (1H, d)

[0130] MS (m / z): 453

[0131] The following compounds were prepared by the same method as Example 2.

[0132]

[0133] Example 3: Preparation of 4-tert-butylacenaphthene (16)

[0134] To 15.00 g (97.3 mmol) of acenaphthene in dichloromethane was added 0.65 g (4.9 mmol) of aluminum chloride and stirred for 30 minutes, and then 13.33 g (97.3 mmol) of tert-butyl bromide was slowly added and the reaction was heated to reflux and stirred. Then, distilled water was added to the reaction and stirred for 30 minutes, and then the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was refined by silica gel column chromatography (developing agent: ethyl acetate:n-hexane = 1:4) to obtain 12.03 g (58.8%) of 4-tert-butylacenaphthene (16).

[0135] 1 H NMR (δ ppm ; CDC13): 1.44 (9H, s), 3.32-3.41 (4H, m), 7.11-7.12 (1H, d), 7.29-7.38 (2H, m), 7.76-7.81 (2H, m)

[0136] MS (m / z): 210

[0137] Example 4: Preparation of 3-tert-butyl-5-cyclopropylmethylnaphthalene dicarboxamide trifluoromethanesulfonate (17)

[0138] Reaction 1. Synthesis of 4-tert-butyl-6-cyclopropanecarbonylacenaphthylene

[0139] To 5.0 g (23.8 mmol) of 4-tert-butylacenaphthene (16) in dichloromethane was added 3.33 g (25.0 mmol) of aluminum chloride and stirred for 30 minutes, and then 2.49 g (23.8 mmol) of cyclopropylcarbonyl chloride diluted with dichloromethane was slowly added and the reaction was stirred at 5°C

[0140] for 30 minutes. Then, distilled water was added to the reaction and stirred for 30 minutes, and then the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was refined by silica gel column chromatography (developing agent: ethyl acetate:n-hexane = 1:4) to obtain 5.0 g (72.0%) of 3-tert-butyl-5-cyclopropylmethylnaphthalene dicarboxamide trifluoromethanesulfonate (17).

[0141] The reaction was stirred for 1 hour. Then, distilled water was added to the reaction and stirred for 30 minutes, and then the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was refined by silica gel column chromatography (developing agent: ethyl acetate:n-hexane = 1:4) to obtain 4.56 g (68.9%) of 4-tert-butyl-6-cyclopropanecarbonylacenaphthene.

[0142] 1 H NMR (δ ppm ; CDC13): 1.08-1.02 (2H, m), 1.31-1.35 (2H, m), 1.43 (9H, s), 1.50 (9H, s), 2.63-2.74 (1H, m)), 3.40 (4H, m), 7.34-7.36 (1H, d), 7.53-7.54 (1H, d), 8.11-8.13 (1H, d), 8.39-8.40 (1H, d)

[0143] MS (m / z): 278

[0144] Reaction 2. Synthesis of 4-tert-butyl-6-cyclopropylmethylacenaphthylene

[0145] The reaction was stirred for 1 hour. Then, distilled water was added to the reaction and stirred for 30 minutes, and then the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was refined by silica gel column chromatography (developing agent: ethyl acetate:n-hexane = 1:4) to obtain 4.56 g (68.9%) of 4-tert-butyl-6-cyclopropanecarbonylacenaphthene.

[0146] 1 H NMR (δ ppmH NMR (CDCI3): 0.23-0.27 (2H, m) 0.52-0.56 (2H, m), 1.12-1.20 (IH, m), 1.50 (9H, s), 2.93-2.94 (2H, d) 3.35-3.42 (4H, m), 7.25-7.26 (IH, d), 7.32-7.33 (IH, d), 7.40-7.41 (IH, d), 7.66-7.67 (IH, d)

[0147] MS (m / z): 264

[0148] Reaction 3. Synthesis of 3-tert-butyl-5-cyclopropylmethyl naphthalene anhydride

[0149] To 10.05 g (38.0 mmol) of 4-tert-butyl-6-cyclopropylmethylnaphthalene in acetic acid was added 56.63 g (190.0 mmol) of sodium dichromate dihydrate, and stirred at normal temperature and heated to reflux. Then, cooled to normal temperature, then removed ethanol under reduced pressure, added ethyl acetate and distilled water and stirred, then separated the organic layer. The separated organic layer was washed with distilled water twice, then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was refined by silica gel column chromatography (developing agent: ethyl acetate:n-hexane = 1:4) to obtain 7.25 g (61.9%) of 3-tert-butyl-5-cyclopropylmethylnaphthalene anhydride.

[0150] 1 H NMR (CDCI3): 0.23-0.27 (2H, m) 0.52-0.56 (2H, m), 1.12-1.20 (IH, m), 1.50 (9H, s), 2.93-2.94 (2H, d) 3.35-3.42 (4H, m), 7.25-7.26 (IH, d), 7.32-7.33 (IH, d), 7.40-7.41 (IH, d), 7.66-7.67 (IH, d) ppm ; CDCI3): 0.31-0.36 (2H, m), 0.64-0.70 (2H, m), 1.14-1.23 (IH, m), 1.50 (9H, s), 3.14-3.16 (2H, d), 7.79-7.81 (IH, d), 8.58-8.60 (IH, d), 8.66-8.68 (IH, d), 8.71-8.72 (IH, d)

[0151] MS (m / z): 308

[0152] Reaction 4. Synthesis of N-hydroxy-3-tert-butyl-5-cyclopropylmethyl naphthalene dicarboxamide

[0153] To 10.80 g (35.0 mmol) of 3-tert-butyl-5-cyclopropylmethyl naphthalene anhydride in ethanol was added 3.65 g (52.5 mmol) of hydroxylamine hydrochloride and 4.16 g (52.5 mmol) of pyridine and heated to reflux. Ethanol was removed by reduced pressure, ethyl acetate and distilled water were added and stirred, and then the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was refined by silica gel column chromatography (developing solvent: ethyl acetate : n-hexane = 1 : 4) to obtain 8.23 g (72.7%) of N-hydroxy-3-tert-butyl-5-cyclopropylmethyl naphthalene dicarboxamide.

[0154] 1 H NMR (δ ppm ; CDC13): 0.30-0.34 (2H, m), 0.64-0.69 (2H, m), 1.12-1.21 (1H, m), 1.50 (9H, s), 3.14-3.16 (2H, d), 7.74-7.76 (1H, d), 8.57-8.59 (1H, d), 8.69-8.71 (1H, d) 8.76-8.77 (1H, d), 8.79 (1H, b)

[0155] MS (m / z): 323

[0156] Reaction 5. Synthesis of 3-tert-butyl-5-cyclopropylmethyl naphthalene dicarboxamide trifluoromethanesulfonate (17)

[0157] To 10.65 g (32.9 mmol) of N-hydroxy-3-tert-butyl-5-cyclopropylmethyl naphthalene dicarboxamide in dichloromethane was added 6.66 g (65.9 mmol) of triethylamine and stirred for 30 minutes and cooled to below 5°C. 5.55 g (32.9 mmol) of trifluoromethanesulfonyl chloride was added, and then stirred at normal temperature. Then, distilled water was added and stirred, and then the organic layer was separated. The separated organic layer was washed with distilled water twice, and then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was refined by silica gel column chromatography (developing solvent: ethyl acetate : n-hexane = 1 : 4) to obtain 10.55 g (70.3%) of 3-tert-butyl-5-cyclopropylmethyl naphthalene dicarboxamide trifluoromethanesulfonate (17).

[0158] 1 H NMR (δ ppm; CDC13): 0.31-0.35 (2H, m), 0.65-0.70 (2H, m), 1.13-1.21 (IH, m), 1.50 (9H, s), 3.15-3.16 (2H, d), 7.77-7.79 (IH, d), 8.61-8.62 (IH, d), 8.70-8.72 (IH, d), 8.77-8.78 (IH, d)

[0159] MS (m / z): 455

[0160] The following compounds were prepared by the same method as in Example 4.

[0161]

[0162] Preparation of binder resin

[0163] a) Preparation of Adhesive Resin 1

[0164] In a 500-ml polymerization vessel, 200 ml of propylene glycol monomethyl ether acetate (PGMEA) and 1.5 g of azobisisobutyronitrile (AIBN) were added, and then acetoxy styrene, styrene and t-butyl methacrylate were added in a molar ratio of 50:25:25, respectively, so as to make the solid content 40% by weight, and then stirred and polymerized at 70°C for 5 hours under a nitrogen atmosphere, thereby preparing an adhesive resin 1. The weight average molecular weight of the copolymer prepared as described above was confirmed to be 25,000, and the dispersity was 2.0.

[0165] b) Preparation of Adhesive Resin 2

[0166] In a 500-ml polymerization vessel, 200 ml of PGMEA and 1.5 g of AIBN were added, and then acetoxy styrene, styrene, t-butyl methacrylate and methyl methacrylate were added in a molar ratio of 40:25:25:10, respectively, so as to make the solid content 40% by weight, and then stirred and polymerized at 70°C for 5 hours under a nitrogen atmosphere, thereby synthesizing a copolymer. In the reactor, 0.3 g of N,N-dimethylaniline and 20 molar ratio of glycidyl methacrylate were added, and then stirred at 100°C for 10 hours, thereby preparing an adhesive resin 2 which is an acrylic polymer having an acrylic unsaturated bond in a side chain. The weight average molecular weight of the copolymer prepared as described above was confirmed to be 20,000, and the dispersity was 2.1.

[0167] Measurement of solubility

[0168] In preparing a photoresist composition, solubility of a photoacid generator is very important. Therefore, solubility in propylene glycol monomethyl ether acetate (PGMEA) and cyclohexane, which are used as solvents mainly in a photoresist composition, was compared and measured with respect to the compound of the following Chemical Formula V, and is shown in Table 1 below.

[0169] [Chemical Formula V]

[0170]

[0171] [Table 1] Solubility of photoacid generator

[0172]

[0173] Measurement of thermal stability

[0174] When a photoacid generator has thermal stability in a preparation process of a photoresist, a very excellent effect can be expected in stability. Therefore, using a thermogravimetric analyzer, a temperature at which 5% of weight loss occurs was compared and measured with respect to the compound of the following Chemical Formula V.

[0175] [Table 2] Thermal stability of photoacid generator

[0176] Compound No. Temperature at which 5% weight loss occurs (°C) 1 242 5 252 9 258 13 244 19 236 Chemical Formula V 223

[0177] Preparation of photoresist compositions of Examples

[0178] According to the components and contents described in Table 3 below, a binder resin 1 to a binder resin 2, a compound 1, a compound 2, a compound 4, a compound 11, a compound 18, and FC-430 (a leveling agent of 3M Company, 0.02% by weight) as a photoacid generator were sequentially added in a reaction mixing tank provided with an ultraviolet ray shielding film and a stirrer, and PGMEA as a solvent was added to be 100% by weight while stirring at room temperature, thereby preparing a photoresist composition.

[0179] [Table 3] Preparation of photoresist composition

[0180]

[0181] Preparation of photoresist compositions of Comparative Examples

[0182] A photoresist composition was prepared by the same method as the preparation of the composition 1, except that a photoacid generator of the following Chemical Formula V was used instead of the compound 5 as a photoacid generator.

[0183] [Chemical Formula V]

[0184]

[0185] Evaluation of photoresist compositions

[0186] The photoresist compositions of the Examples and the Comparative Examples were evaluated on a glass substrate, the pattern stability and taper angle of the photoresist compositions were measured, and the results of the evaluation thereof are shown in Table 4 below.

[0187] 1) Pattern stability

[0188] The photoresist was spin-coated on a silicon wafer substrate, dried on a hot plate at 90°C for 1 minute, then exposed using a line width-space (10 μm-10 μm) step mask, then developed in a 2.384% aqueous solution of trimethylammonium hydroxide (TMAH) after a post-exposure bake process. The width of the pattern of the space part was measured after development.

[0189] 2) Taper angle

[0190] The photoresist was spin-coated on a silicon wafer substrate, dried on a hot plate at 90°C for 1 minute, then exposed using a line width-space (10 μm-10 μm) step mask, then developed in a 2.384% aqueous solution of TMAH after a post-exposure bake process. The taper angle of the space part was measured after development, and when the taper angle was 85° to 90°, it was determined to be good, and when the taper angle was less than 85° or more than 91°, it was determined to be poor.

[0191] [Table 4]

[0192]

[0193]

Claims

1. A naphthalimide sulfonic acid ester derivative compound represented by the following Chemical Formula I or Chemical Formula II: [Chemical Formula I] [Chemical Formula II] In the Chemical Formula II, R1, m and n are the same as defined in the Chemical Formula I, and R2 is a hydrogen atom. ， In the formula I, R1is a C1-C 12 linear alkyl group or a C3-C 12 branched alkyl group; a C3-C 12 alicyclic hydrocarbon group; an unsubstituted C6-C 20 aryl group; or a C7-C 20 alkylaryl group; R2is a hydrogen atom or a tert-butyl group; m is an integer of 1 to 4; and n is an integer of 0 to 2. R1 is a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a nonafluorobutyl group or a tolyl group. ， The naphthalimide sulfonic acid ester derivative compound is selected from the following compounds:

2. The naphthalimide sulfonate derivative compound according to claim 1, wherein, 4. A photo-acid generator comprising the naphthalimide sulfonic acid ester derivative compound according to any one of claims 1 to 3.

3. The naphthalimide sulfonate derivative compound according to claim 1, wherein, 5. A photoresist composition comprising the naphthalimide sulfonic acid ester derivative compound according to any one of claims 1 to 3 and a binder resin. 。 6. An acenaphthene derivative compound represented by the following Chemical Formula III or Chemical Formula IV: [Chemical Formula III] In the Chemical Formula III, R2 is a hydrogen atom or a tert-butyl group; m is an integer of 1 to 4; and n is an integer of 0 to 2. [Chemical Formula IV] In the Chemical Formula IV, R2 is a hydrogen atom; and m and n are the same as defined in the Chemical Formula III. The preparation method comprises a step of reducing the following Chemical Formula III' or Chemical Formula IV' respectively: ， [Chemical Formula III'] [Chemical Formula IV'] In the Chemical Formula III' and Chemical Formula IV', R2, m and n are the same as defined in the Chemical Formula III and Chemical Formula IV of claim 6, respectively. ​ ， ​ 7. A method for preparing a acenaphthene derivative compound represented by chemical formula III or chemical formula IV as described in claim 6, wherein, ​ ​ ， ​ ， ​

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