Novel sulfonic acid derivative of naphthalimide, and photoacid generator and photoresist composition containing the same

Abstract

The present invention relates to a naphthalimide sulfonic acid derivative, and a photoacid generator and a photoresist composition containing the same; more specifically, the present invention relates to a naphthalimide sulfonic acid derivative compound which has excellent absorbance for light of an i-line wavelength (365 nm) and has extremely high solubility in organic solvents, making it very easy to prepare a polymerizable composition therewith, has good thermal stability, and exhibits a good acid generation rate, as well as a photoacid generator and a photoresist composition containing the same.

Description

[Technical field]

[0001] The present invention relates to a naphthalimide sulfonic acid derivative, and a photoacid generator and photoresist composition containing the same; more specifically, the present invention relates to a naphthalimide sulfonic acid derivative compound that has excellent absorbance for light of i-line wavelength (365 nm) and has extremely high solubility in organic solvents, making it very easy to prepare a polymerizable composition therewith, has good thermal stability, and exhibits a good acid generation rate, as well as a photoacid generator and photoresist composition containing the same. [Background technology]

[0002] A photoacid generator is a compound that generates an acid upon irradiation with light, and the acid generated therefrom decomposes some of the components in the photoresist composition or causes a crosslinking reaction, thereby changing the polarity of the polymer in the composition. This change in the polarity of the polymer causes a difference in solubility in a developer between the exposed and unexposed areas, which results in positive or negative lithography.

[0003] In the case of a photoresist composition, the photoacid generator therein should have good energy sensitivity to irradiated light so that a fine pattern can be formed. However, when a conventional photoacid generator is used alone, there is a problem that the sensitivity of the photoresist cannot be sufficiently increased.

[0004] Therefore, there is a demand for the development of a photoacid generator that has excellent photosensitivity that provides sufficient sensitivity even with a small amount, and that can reduce costs and increase production by reducing the exposure dose due to its excellent sensitivity. In addition, there is an advantage that the solubility of the photoacid generator in the main solvent of the photoresist is improved, making it easier to prepare each composition.

[0005] Various developments have been made on naphthalimide compounds to improve their photosensitivity and solubility. For example, Patent Document 1 discloses the preparation of naphthalimide compounds using a cryogenic condition of -70°C and a metal compound such as 1-butyllithium, and Patent Documents 2 and 3 disclose the preparation of naphthalimide compounds using a bromine-substituted compound. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Korea Patent No. 10-2017-0125980 [Patent Document 2] Korea Patent No. 10-2017-0042726 [Patent Document 3] Korea Patent No. 10-2012-0114353 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a sulfonic acid derivative compound of naphthalimide which has excellent photosensitivity and high solubility in organic solvents, is excellent in thermal stability, and exhibits a good acid generation rate, and which is suitable as a photoacid generator for use in photolithography, and to provide a photoacid generator and a photoresist composition containing the same. [Means for solving the problem]

[0008] In order to achieve the above object, the first aspect of the present invention provides a compound represented by the following formula (I):

[0009] [ka]

[0010] [In the formula, R1 and R2 each independently represent 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; Each R3 is independently a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted alkylaryl group, or a group of the formula R4-O-(CH2) n - (wherein n=1 to 12, and R4 is a substituted or unsubstituted aliphatic hydrocarbon group). The present invention provides a sulfonic acid derivative compound of naphthalimide represented by the following formula:

[0011] A second aspect of the present invention provides a photoacid generator comprising the naphthalimide sulfonic acid derivative compound of the present invention.

[0012] A third aspect of the present invention provides a photoresist composition comprising the naphthalimide sulfonic acid derivative compound of the present invention and a binder resin.

[0013] In another aspect of the present invention, there are provided a substrate coated with the photoresist composition of the present invention; a patterned substrate obtained by exposing and developing the coated substrate; a display device comprising the patterned substrate; and a semiconductor device comprising the patterned substrate. Effect of the Invention

[0014] The naphthalimide sulfonic acid derivative compound of the present invention has high solubility in photoresist solvents, excellent thermal stability, and extremely excellent sensitivity to light for photolithography (for example, light with an i-line (365 nm) wavelength). Therefore, by using it as a photoacid generator component of a photoresist composition, even when used in a small amount, it is possible to provide a pattern with excellent developability, taper angle, pattern stability, etc., and further, since gas emission from the photoacid generator during the exposure and post-bake steps can be minimized, there is an advantage in that contamination can be reduced and defects that may occur as a result can be minimized. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present invention will be described in detail below.

[0016] The sulfonic acid derivative compound of the naphthalimide of the present invention is represented by the following formula (I):

[0017] [ka]

[0018] [In the formula, R1 and R2 each independently represent 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; Each R3 is independently a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted alkylaryl group, or a group of the formula R4-O-(CH2) n -(wherein n=1 to 12, and R4 is a substituted or unsubstituted aliphatic hydrocarbon group).

[0019] More specifically, in formula (I): The R1 and R2 are each independently a substituted or unsubstituted C1 to C12 or a straight chain alkyl group of C3 to C 12 Branched alkyl groups; substituted or unsubstituted C3-C 12 Alicyclic hydrocarbon groups; substituted or unsubstituted C6-C 20 aryl groups; substituted or unsubstituted C7-C 20 or a substituted or unsubstituted C7-C 20 an alkylaryl group of the formula:

[0020] The R3 is a substituted or unsubstituted C1 to C 12 or a straight chain alkyl group of C3 to C 12 Branched alkyl groups; substituted or unsubstituted C3-C 12 Alicyclic hydrocarbon groups; substituted or unsubstituted C6-C 20 aryl groups; substituted or unsubstituted C7-C 20 arylalkyl groups; substituted or unsubstituted C7-C 20 or a substituted or unsubstituted C1-C 12 Alkoxy-C1~C 12 It may be an alkyl group.

[0021] More specifically, in formula (I): The R1 and R2 each independently represent a C1 to C6 alkyl group which is unsubstituted or substituted with one or more halogen atoms or alicyclic hydrocarbon groups. 12 or a straight chain alkyl group of C3 to C 12 A branched alkyl group of C3-C, substituted or unsubstituted with one or more halogen atoms. 12 Alicyclic hydrocarbon groups; C6-C substituted or unsubstituted with one or more halogen atoms 20 an aryl group; one or more halogen atoms or C1-C 12 C7-C substituted or unsubstituted alkylthio groups 20 or an arylalkyl group having one or more halogen atoms; 20 an alkylaryl group of the formula:

[0022] The R3 is a C1-C substituted or unsubstituted group having one or more halogen atoms or alicyclic hydrocarbon groups. 12 or a straight chain alkyl group of C3 to C 12 A branched alkyl group of C3-C, substituted or unsubstituted with one or more halogen atoms. 12 Alicyclic hydrocarbon groups; C6-C substituted or unsubstituted with one or more halogen atoms 20 an aryl group; one or more halogen atoms or C1-C 12 C7-C substituted or unsubstituted alkylthio groups 20 Arylalkyl groups of C7-C, substituted or unsubstituted with one or more halogen atoms. 20 or an alkylaryl group having one or more halogen atoms; 12 an alkoxy-C1-C4 alkyl group;

[0023] More specifically, R1 may be a methyl group, an ethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a nonafluorobutyl group, or a tosyl group;

[0024] R2 may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a cyclohexyl group;

[0025] The R3 may be a methyl group, an ethyl group, a propyl group, a hexyl group, a heptyl group, a cyclohexyl group, a methoxyethyl group, or a butoxyethyl group.

[0026] In the present invention, the substituents containing the "alkyl" moiety include all forms, linear or branched, and "cycloalkyl" includes monocyclic as well as polycyclic hydrocarbons. In the present invention, "aryl" refers to an organic group derived from an aromatic hydrocarbon by removing one hydrogen, and includes monocyclic or fused ring systems, suitably containing 4 to 7, preferably 5 or 6 ring atoms in each ring, as well as forms in which multiple aryls are linked by single bonds. In the present invention, C1 to C12 The alkyl group is more specifically C1-C 10 Alkyl, more specifically C1-C6 alkyl, C6-C 20 The aryl group is more specifically a C6-C 18 Aryl, C3-C 12 The cycloalkyl group is more specifically a C3-C 10 It may also be cycloalkyl.

[0027] In one embodiment, the naphthalimide sulfonic acid derivative compound of the present invention can be selected from, but is not limited to, the following compounds:

[0028] [ka]

[0029] In one embodiment, the sulfonic acid derivative compound of naphthalimide of formula (I) according to the present invention can be prepared through a route as shown in the following reaction scheme 1, but is not limited thereto.

[0030] <Reaction Scheme 1> [ka] [In the formula, R1 to R3 are defined as in formula (I).]

[0031] The naphthalimide sulfonic acid derivative compound of the present invention has high solubility in photoresist solvents, excellent thermal stability, and extremely excellent sensitivity to light for photolithography, and is therefore extremely useful as a photoacid generator component in a photoresist composition.

[0032] Thus, another aspect of the present invention provides photoacid generators and photoresist compositions that include the naphthalimide sulfonic acid derivative compounds of the present invention.

[0033] The photoresist composition of the present invention comprises the sulfonic acid derivative compound of naphthalimide of the present invention and a binder resin, and the sulfonic acid derivative compound of naphthalimide is contained as a photoacid generating component.

[0034] In one embodiment, the binder resin is 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 hydroxystyrene, acrylic acid, methacrylic acid, and their derivatives; a copolymer of two or more monomers selected from hydroxystyrene, styrene, and their derivatives; a copolymer of three or more monomers selected from cycloolefin, maleic anhydride, acrylic acid, and their derivatives; a copolymer of three or more monomers selected from cycloolefin, maleimide, acrylic acid, and their derivatives; polynorbornene; a metathesis ring-opening polymer; and a polymer partially substituted with an acid labile group having an ability to control alkali dissolution; and combinations thereof, but are not particularly limited thereto. Examples of the acid labile group introduced into the polymer include a tertiary alkyl group, a trialkylsilyl group, an oxoalkyl group, an aryl-substituted alkyl group, a heteroalicyclic group such as a tetrahydropyran-2-yl group, a tertiary alkylcarbonyl group, a tertiary alkylcarbonylalkyl group, and an alkyloxycarbonyl group.

[0035] In one embodiment, the binder resin is 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 hydroxystyrene, acrylic acid, methacrylic acid, and derivatives thereof; a copolymer of two or more monomers selected from hydroxystyrene, styrene, and derivatives thereof; a copolymer of three or more monomers selected from hydroxystyrene, styrene, acrylic acid, olefin, cycloolefin, maleic anhydride, and derivatives thereof; and combinations thereof, but are not particularly limited thereto.

[0036] In one embodiment, the “derivative” is, for example, an alkyl or alkoxy substituted derivative of the original compound (more specifically, C1-C 10 or, if the original compound is an acid compound, the alkyl (more specifically, C1-C 10 The alkyl ester may be, but is not limited to, an alkyl ester.

[0037] In one embodiment, the binder resin may be, for example, a copolymer of two or more monomers selected from the following monomers:

[0038] 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, tetradecyl (meth)acrylate and hexadecyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate acrylate, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, itaconate monoalkyl, fumarate monoalkyl, 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., as well as styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth)acrylamide, N-methyl(meth)acrylamide.

[0039] In one embodiment, the binder resin may be a polymer having an acrylic unsaturated bond in a side chain, for example, a copolymer obtained by addition reaction of an epoxy compound to a copolymer containing a carboxylic acid.

[0040] More specifically, the copolymer containing a carboxylic acid is a copolymer containing a monomer containing a carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or a maleic acid monoalkyl ester, and an alkyl (meth)acrylate such as methyl (meth)acrylate or hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, styrene, α-methylstyrene, or acetoxystyrene. The carboxylic acid-containing copolymer can be obtained by copolymerizing one or more monomers such as butylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth)acrylamide, and N-methyl(meth)acrylamide. The copolymer obtained by addition reaction of such a carboxylic acid-containing copolymer with an epoxy compound 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 to 180°C can be used as the binder resin.

[0041] In one embodiment, the weight average molecular weight of the binder resin is 2,000 to 300,000, more specifically 4,000 to 100,000, and the dispersity thereof may be 1 to 10, but is not particularly limited thereto.

[0042] In one embodiment, the sulfonic acid derivative compound of naphthalimide used as a photoacid generator in order to enhance developability and minimize the exposure dose is in the range of 0.01 to 10 wt %, 0.01 to 9 wt %, 0.01 to 8 wt %, 0.01 to 7 wt %, 0.01 to 6 wt %, 0.01 to 5 wt %, 0.01 to 4 wt %, 0.01 to 3 wt %, 0.01 to 2 wt %, 0.01 to 1 wt %, 0.01 to 0.5 wt %, 0.01 to 0.4 wt %, 0.01 to 0.35 wt %, 0.01 to 0.3 wt %, 0.01 to 0.2 wt %, based on 100 wt % of the photoresist composition of the present invention. Amount%, 0.05~10 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. 1~1wt%, 0.1~0.5wt%, 0.1~0.4wt%, 0.1~0.35wt%, 0.1~0.3wt%, 0.1~0.2wt%, 0.2~10wt%, 0.2~9wt%, 0.2~8wt%, 0.2~7wt%, 0.2~6wt%, 0.2~5wt%, 0.2~4wt% Amount%, 0.2~3wt%, 0.2~2wt%, 0.2~1wt%, 0.2~0.5wt%, 0.2~0.4wt%, 0.2~0.35wt%, 0.2~0.3wt%, 0.25~10wt%, 0.25~9wt%, 0.25~8wt%, 0.25~7wt%, 0.25~6wt %, 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.It may be contained in an amount of 35 to 8% by weight, 0.35 to 7% by weight, 0.35 to 6% by weight, 0.35 to 5% by weight, 0.35 to 4% by weight, 0.35 to 3% by weight, 0.35 to 2% by weight, 0.35 to 1% by weight, 0.35 to 0.5% by weight, 0.35 to 0.4% by weight, 0.4 to 10% by weight, 0.4 to 9% by weight, 0.4 to 8% by weight, 0.4 to 7% by weight, 0.4 to 6% by weight, 0.4 to 5% by weight, 0.4 to 4% by weight, 0.4 to 3% by weight, 0.4 to 2% by weight, 0.4 to 1% by weight, or 0.4 to 0.5% by weight, more specifically, it may be contained in an amount of 0.1 to 5% by weight, but is not particularly limited thereto.

[0043] In one embodiment, in order to control pattern characteristics and impart thin film properties, the binder resin is, for example, 30 to 99% by weight, 35 to 99% by weight, 40 to 99% by weight, 45 to 99% by weight, 50 to 99% by weight, 30 to 97% by weight, 35 to 97% by weight, 40 to 97% by weight, 45 to 97% by weight, 50 to 97% by weight, 30 ~95wt%, 35~95wt%, 40~95wt%, 45~95wt%, 50~95wt%, 30~93wt%, 35~93wt%, 40~93wt%, 45~93wt%, 50~9 3wt%, 30~90wt%, 35~90wt%, 40~90wt%, 45~90wt%, 50~90wt%, 30~85wt%, 35~85wt%, 40~85wt%, 45~85wt Amount%, 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% by weight, 50~75% by weight, 30~70% by weight, 35~70% by weight, 40~70% by weight, 45~70% by weight, 50~70% by weight, 30~65% by weight, 35~65% by weight, 4 It may be included in an amount of 0 to 65% by weight, 45 to 65% by weight, 50 to 65% by weight, 30 to 60% by weight, 35 to 60% by weight, 40 to 60% by weight, 45 to 60% by weight, 50 to 60% by weight, 30 to 55% by weight, 35 to 55% by weight, 40 to 55% by weight, 45 to 55% by weight, or 50 to 55% by weight, or more specifically, it may be included in an amount of 50 to 99% by weight, but is not particularly limited to these.

[0044] The photoresist composition of the present invention may further comprise a solvent.

[0045] As the solvent, taking into consideration the compatibility with the photoacid generator and other compounds, 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 methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isopropyl alcohol, ethyl ethyl ether, ethyl butyl alcohol ... Solvents such as isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether, ethylene 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, and octane can be used alone or in combination of two or more.

[0046] In one embodiment, the solvent may be contained in an amount of, for example, 0.9 to 60% by weight relative to 100% by weight of the photoresist composition of the present invention in order to adjust the viscosity of the composition to within the range of 1 to 50 cps, but is not particularly limited thereto.

[0047] The photoresist composition of the present invention may optionally further contain compatible additives such as an antifoaming agent, a leveling agent, and the like.

[0048] Further aspects of the present invention provide a substrate coated with the photoresist composition of the present invention; a patterned substrate obtained by exposing and developing the coated substrate; a display device comprising the patterned substrate; and a semiconductor device comprising the patterned substrate.

[0049] In one embodiment, the substrate may be, for example, a silicon wafer substrate, the coating of the photoresist composition may be performed by a known method such as, for example, spin coating, the exposure may be performed using, for example, i-line (365 nm) wavelength light, and the development may be performed using, for example, a basic developer such as, but not limited to, an aqueous solution of trimethylammonium hydroxide (TMAH).

[0050] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited thereto in any way. EXAMPLES

[0051] Example 1: Preparation of 4-(1-ethoxybutyl)-naphthalimide trifluoromethanesulfonate (1) Reaction 1. Synthesis of 5-butyrylacenaphthene 21.43g (139.0mmol) of acenaphthene was added to dichloromethane and cooled to below 10°C. 19.46g (145.9mmol) of aluminum chloride was added thereto and stirred for 30 minutes, after which 14.81g (139.0mmol) of butyryl chloride was slowly added and the reaction mixture was stirred at below 5°C for 1 hour. Purified water was then added to the reaction product and stirred for 30 minutes, after which the organic layer was separated. The separated organic layer was washed twice with purified water, and the collected organic layer was dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The concentrated residue was purified by silica gel column chromatography (developing solvent: ethyl acetate: n-heptane = 1:4) to obtain 21.90g (70.26%) of 5-butyrylacenaphthene. 1H NMR(δppm;CDCl3):δ8.65-8.62(dd,1H),8.05-8.02(d,1H),7.66-7.55(dd,1H),7.41-7.35 (d,1H),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) MS(m / z): 224

[0052] Reaction 2. Synthesis of 5-(1-ethoxybutyl)acenaphthene 10.60g (47.3mmol) of 5-butyrylacenaphthene was dissolved in ethanol, sodium borohydride was added, and the mixture was stirred at 60°C. The mixture was then cooled to below 10°C, and 19.17mL of 10% aqueous hydrochloric acid was slowly added and stirred at 60°C. After the reaction was completed, purified water was added to the reaction product and stirred for 30 minutes. Ethyl acetate was then added and stirred, and the organic layer was separated. The separated organic layer was washed with a saturated aqueous sodium bicarbonate solution and purified water, respectively, and the collected organic layer was dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the solvent. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate: n-heptane = 1:10) to obtain 9.54g (79.3%) of 5-(1-ethoxybutyl)acenaphthene. 1 H NMR(δppm;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) MS(m / z): 254

[0053] Reaction 3. Synthesis of 4-(1-ethoxybutyl)naphthalic anhydride 7.24g (28.4mmol) of 5-(1-ethoxybutyl)acenaphthene was added to acetic acid, 42.41g (142.3mmol) of sodium dichromate dihydrate was added, and the mixture was stirred at room temperature and heated to reflux. 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. After separating the organic layer, it was washed with a saturated aqueous solution of sodium bicarbonate and purified water, and then the collected organic layer was dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the solvent. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate: n-heptane = 1:10) to obtain 6.32g (74.4%) of 4-(1-ethoxybutyl)naphthalic anhydride. 1 H NMR(δppm;CDCl3):δ8.73(dd,1H),8.65(dd,1H),8.62(d,1H),7.87(d,1H),7.83(dd,1H),5.00(dd,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) MS(m / z): 298

[0054] Reaction 4. Synthesis of N-hydroxy-4-(1-ethoxybutyl)naphthalimide 4.60g (15.4mmol) of 4-(1-ethoxybutyl)naphthalic anhydride was added to ethanol, 1.61g (23.1mmol) of hydroxylamine hydrochloride and 1.83g (23.1mmol) of pyridine were added, and the mixture was heated to reflux. Ethanol was removed under reduced pressure to obtain 4.18g (crude yield: 86.5%) of crude N-hydroxy-4-(1-ethoxybutyl)naphthalimide, which was used in the next reaction without further purification. 1H NMR(δppm;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) MS(m / z): 313

[0055] Reaction 5. Synthesis of 4-(1-ethoxybutyl)naphthalimide trifluoromethanesulfonate (1) 4.08g (13.2mmol) of N-hydroxy-4-(1-ethoxybutyl)naphthalimide was added to dichloromethane, 2.64g (26.0mmol) of triethylamine was added, and the mixture was stirred for 30 minutes, then cooled to below 5°C. 2.19g (13.2mmol) of trifluoromethanesulfonyl chloride was added and stirred at room temperature. Next, purified water was added to the reaction product, and after stirring, the organic layer was separated. The separated organic layer was washed twice with purified water, and the collected organic layer was dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the solvent. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate: n-heptane = 1:4) to obtain 4.12g (71.7%) of 4-(1-ethoxybutyl)naphthalimide trifluoromethanesulfonate (1). 1 H NMR(δppm;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) MS(m / z): 445

[0056] The following compounds were prepared in a similar manner to Example 1 above.

[0057] [Table 1-1]

[0058] [Table 1-2]

[0059] Preparation of binder resin a) Preparation of binder resin 1 200 mL of propylene glycol monomethyl ether acetate (PGMEA) and 1.5 g of azobisisobutyronitrile (AIBN) were added to a 500 mL polymerization vessel, and acetoxystyrene, styrene, and t-butoxy methacrylate were added in a molar ratio of 50:25:25 to give a solids concentration of 40% by weight. The mixture was polymerized under stirring at 70°C for 5 hours in a nitrogen atmosphere to prepare binder resin 1. The weight average molecular weight of the copolymer thus prepared was confirmed to be 25,000 and the polydispersity to be 2.0.

[0060] b) Preparation of binder resin 2 200mL of PGMEA and 1.5g of AIBN were added to a 500mL polymerization vessel, and acetoxystyrene, styrene, t-butoxymethacrylate, and methylmethacrylate were added in a molar ratio of 40:25:25:10 to give a solids concentration of 40% by weight. The mixture was stirred and polymerized at 70°C for 5 hours under a nitrogen atmosphere to synthesize a copolymer. 0.3g of N,N-dimethylaniline and 20% by mole of glycidyl methacrylate were added to the reactor and stirred at 100°C for 10 hours to prepare binder resin 2, an acrylic polymer having an acrylic unsaturated bond in the side chain. The weight average molecular weight of the copolymer thus prepared was confirmed to be 20,000 and the dispersity to be 2.1.

[0061] Solubility measurements In the preparation of a photoresist composition, the solubility of a photoacid generator is very important. Therefore, the solubility in propylene glycol monomethyl ether (PGMEA) and cyclohexane, which are solvents mainly used in photoresist compositions, is compared with the compound of formula (II) below and shown in Table 1 below.

[0062] [ka]

[0063] [Table 2]

[0064] Thermal stability measurements If the photoacid generator is thermally stable in the photoresist preparation process, it is expected to have a very excellent effect in terms of stability. Therefore, in order to compare with the compound of formula (II), the temperature at which a 5% weight loss occurs was measured using a thermogravimetric analyzer.

[0065] [Table 3]

[0066] EXAMPLES Preparation of Photoresist Compositions In a reaction mixing tank equipped with an ultraviolet ray blocking film and a stirrer, binder resin 1 or 2; compound 8, 11, 19 or 20 as a photoacid generator; and FC-430 (leveling agent of 3M, 0.02 wt %) were sequentially added in accordance with the components and contents shown in Table 3 below, and after stirring at room temperature, PGMEA was added as a solvent to make the total weight 100 to prepare a photoresist composition.

[0067] [Table 4]

[0068] Preparation of Comparative Photoresist Compositions A photoresist composition was prepared in the same manner as in the preparation of composition 3, except that a photoacid generator represented by the following formula (II) was used instead of compound 19 as the photoacid generator.

[0069] [ka]

[0070] Evaluation of photoresist compositions The photoresist compositions of the above Examples and Comparative Examples were evaluated on a glass substrate, and the pattern stability and taper angle of the photoresist compositions were measured. The evaluation results are shown in Table 4 below.

[0071] 1) Pattern stability The photoresist was spin-coated on a silicon wafer substrate, dried on a hot plate at 90°C for 1 minute, exposed using a line-space (10μm-10μm) step mask, baked after exposure, and developed with a 2.384% trimethylammonium hydroxide (TMAH) aqueous solution. The width of the pattern in the space portion after development was measured.

[0072] 2) Taper angle The photoresist was spin-coated on a silicon wafer substrate, dried on a hot plate at 90°C for 1 minute, exposed using a line-space (10μm-10μm) step mask, baked after exposure, and developed with a 2.384% TMAH aqueous solution. The taper angle of the space portion after development was measured, and a value of 85-90° was judged as good, and a value of less than 85° or more than 91° was judged as bad.

[0073] [Table 5]

Claims

1. The following formula (I) 【Chemistry 1】 [In the formula, R 1 and R 2 each independently represents a substituted or unsubstituted C 1 -C 12 linear alkyl group or C 3 -C 12 branched alkyl group; a substituted or unsubstituted C 3 -C 12 alicyclic hydrocarbon group; a substituted or unsubstituted C 6 -C 20 aryl group; a substituted or unsubstituted C 7 -C 20 arylalkyl group; or a substituted or unsubstituted C 7 -C 20 alkylaryl group; R 3 is a substituted or unsubstituted C 1 -C 12 linear alkyl group or C 3 -C 12 branched alkyl group; a substituted or unsubstituted C 3 -C 12 alicyclic hydrocarbon group; a substituted or unsubstituted C 6 -C 20 aryl group; a substituted or unsubstituted C 7 -C 20 arylalkyl group; a substituted or unsubstituted C 7 -C 20 alkylaryl group; or a substituted or unsubstituted C 1 -C 12 alkoxy-C 1 -C 12 alkyl group. A sulfonic acid derivative compound of naphthalimide represented by the formula:

2. R 1 and R 2 each independently represents one or more halogen atoms or alicyclic hydrocarbon groups, or a substituted or unsubstituted C 1 ~C 12 or a linear alkyl group of C 3 ~C 12 a branched alkyl group of the formula: 3 ~C 12 an alicyclic hydrocarbon group of the formula: 6 ~C 20 an aryl group of the formula: 1 ~C 12 C 7 ~C 20 or an arylalkyl group of the formula: 7 ~C 20 an alkylaryl group of the formula: R 3 C is substituted or unsubstituted with one or more halogen atoms or alicyclic hydrocarbon groups; 1 ~C 12 or a linear alkyl group of C 3 ~C 12 a branched alkyl group of the formula: 3 ~C 12 an alicyclic hydrocarbon group of the formula: 6 ~C 20 an aryl group of the formula: 1 ~C 12 C 7 ~C 20 arylalkyl groups of the formula: 7 ~C 20 or an alkylaryl group of the formula: 1 ~C 12 Alkoxy-C 1 ~C 4 The sulfonic acid derivative compound of claim 1, wherein the naphthalimide is an alkyl group.

3. R 1 is a methyl group, an ethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a nonafluorobutyl group, or a tosyl group, R 2 is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, an octyl group, or a cyclohexyl group, R 3 The sulfonic acid derivative compound of naphthalimide according to claim 1, wherein is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a heptyl group, a cyclohexyl group, a methoxyethyl group (CH3-O-CH2CH2-), or a butoxyethyl group (CH3CH2CH2CH2-O-CH2CH2-).

4. The sulfonic acid derivative compound of claim 1 is selected from the following compounds: 【Chemistry 2】

5. A photoacid generator comprising the naphthalimide sulfonic acid derivative compound according to any one of claims 1 to 4.

6. The sulfonic acid derivative compound of naphthalimide according to any one of claims 1 to 4; and Binder resin; 1. A photoresist composition comprising:

7. A substrate coated with the photoresist composition of claim 6.

8. A patterned substrate obtained by exposing and developing the coated substrate according to claim 7.

9. A display device comprising the patterned substrate of claim 8.

10. A semiconductor device comprising the patterned substrate according to claim 8.

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