US-12624007-B2 - Naphthalimide sulfonate derivative, and photoacid generator and photoresist composition which comprise same

Abstract

The present invention relates to a naphthalimide sulfonate derivative, and a photoacid generator and a photoresist composition which comprise same, and, more specifically, to a naphthalimide sulfonate derivative compound, and a photoacid generator and a photoresist composition which comprise same, the compound having an excellent absorbance of light with an i-line wavelength (365 nm), having a high solubility in an organic solvent, having excellent thermal stability, and exhibiting a good acid generation rate.

Inventors

• Chun Rim Oh
• Dae Hyuk CHOI
• Min Jung Kim
• Deuk Rak LEE
• Won Jung LEE
• Yu Na CHOI
• Ji Eun CHOI

Assignees

• SAMYANG CORPORATION

Dates

Publication Date

20260512

Application Date

20210929

Priority Date

20200929

Claims (6)

1. 1 . A naphthalimide sulfonic acid derivative compound represented by the following Formula I or II: wherein, in Formula I, R 1 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; R 2 is hydrogen atom or t-butyl group; m is an integer of 1 to 4; n is an integer of 0 to 2; wherein, in Formula II, R 1 , m and n are the same as defined in Formula I, and R 2 is hydrogen atom.
2. 2 . The naphthalimide sulfonic acid derivative compound of claim 1 , wherein R 1 is a C 1 -C 12 linear alkyl group or C 3 -C 12 branched alkyl group that is unsubstituted or substituted with one or more halogen atoms or alicyclic hydrocarbon group; a C 3 -C 12 alicyclic hydrocarbon group that is unsubstituted or substituted with one or more halogen atoms; a C 6 -C 20 aryl group that is unsubstituted or substituted with one or more halogen atoms; a C 7 -C 20 arylalkyl group that is unsubstituted or substituted with one or more halogen atoms or C 1 -C 12 alkylthio group; or a C 7 -C 20 alkylaryl group that is unsubstituted or substituted with one or more halogen atoms.
3. 3 . The naphthalimide sulfonic acid derivative compound of claim 1 , wherein R 1 is methyl group, ethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, nonafluorobutyl group or tosyl group.
4. 4 . The naphthalimide sulfonic acid derivative compound of claim 1 , which is selected from the following compounds:
5. 5 . A photoacid generator comprising a naphthalimide sulfonic acid derivative compound of claim 1 .
6. 6 . A photoresist composition comprising a naphthalimide sulfonic acid derivative compound of claim 1 ; and a binder resin.

Description

TECHNICAL FIELD The present invention relates to a naphthalimide sulfonic acid derivative, and a photoacid generator and a photoresist composition comprising the same, and more specifically, the present invention relates to a naphthalimide sulfonic acid derivative compound which has an excellent absorbance of light with i-line wavelength (365 nm) and a high solubility in an organic solvent, and exhibits excellent thermal stability and good acid generation rate, and a photoacid generator and a photoresist composition comprising the same. BACKGROUND ART A photoacid generator is a compound that generates an acid by light irradiation, and the acid generated therefrom—according to the components in a photoresist composition— decomposes a part of the components in the composition or causes crosslinking reaction, to generate change in polarity of polymer in the composition. Such a change in polarity of polymer brings difference in solubility to developer solution between the exposed part and the unexposed part, and as a result, positive or negative lithography becomes possible. For a photoresist composition, the photoacid generator therein should have good energy sensitivity to the irradiated light so that micropatterns can be formed. However, use of conventional photoacid generator alone has a problem that the sensitivity of photoresist cannot be increased satisfactorily. Therefore, it is necessary to develop a photoacid generator which has excellent photosensitivity so as to realize sufficient sensitivity even with a small amount, and thus can reduce exposure dose and increase production due to cost reduction and excellent sensitivity. In addition, improvement in solubility of photoacid generator to the main solvent of photoresist has the advantage of facilitating preparation of various compositions. Various developments for naphthalimide compound have been made in order to increase photosensitivity and improve solubility thereof. For instance, Korean Laid-open Patent Publication No. 10-2017-0125980 discloses preparation of naphthalimide compound by using a cryogenic condition of −70° C. and metal compound such as 1-butyl lithium, and Korean Laid-open Patent Publication No. 10-2017-0042726 and Korean Laid-open Patent Publication No. 2012-0114353 disclose preparation of naphthalimide compound by using bromine-substituted compound. Problems to be Solved The purpose of the present invention is to provide a naphthalimide sulfonic acid derivative compound which has an excellent absorbance of light with i-line wavelength (365 nm) and a high solubility in an organic solvent, and exhibits excellent thermal stability and good acid generation rate, and a photoacid generator and a photoresist composition comprising the same. Technical Means In order to achieve the above-stated purpose, the 1st aspect of the present invention provides a naphthalimide sulfonic acid derivative compound represented by the following Formula I or II: wherein, in 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 hydrogen atom or t-butyl group; m is an integer of 1 to 4; n is an integer of 0 to 2; wherein, in Formula II, R1, m and n are the same as defined in Formula I, and R2 is hydrogen atom. The 2nd aspect of the present invention provides a photoacid generator comprising the naphthalimide sulfonic acid derivative compound of the present invention. The 3rd aspect of the present invention provides a photoresist composition comprising the naphthalimide sulfonic acid derivative compound of the present invention; and a binder resin. The 4th aspect of the present invention provides an acenaphthene derivative compound represented by the following Formula III or IV: wherein, in Formula III, R2 is hydrogen atom or t-butyl group; m is an integer of 1 to 4; n is an integer of 0 to 2; wherein, in Formula IV, R2 is hydrogen atom; and m and n are the same as defined in Formula III. The 5th aspect of the present invention provides a method for preparing an acenaphthene derivative compound represented by the above Formula III or IV, comprising a step of reducing a compound represented by the following Formula III′ or IV′: wherein, in Formulas III′ and IV′, R2, m and n are the same as defined in Formulas III and IV′, respectively. Effect of the Invention The naphthalimide sulfonic acid derivative compound of the present invention has high solubility in a solvent for photoresist, excellent thermal stability, and very excellent sensitivity to light for photoresist (for example, light with i-line wavelength (365 nm)), and thus, when used as a photoacid generator component in a photoresist composition, it can provide patterns having excellent developability, taper angle, pattern stability, etc. even with a small amount of use, and it also can minimize the outgassing generated from photoacid g