US-12625427-B2 - Naphthalimide sulfonate derivative, and photoacid generator and photoresist composition each comprising same

Abstract

The present invention relates to a naphthalimide sulfonate derivative, and a photoacid generator and a photoresist composition each comprising same and, more specifically, to a naphthalimide sulfonate derivative compound, and a photoacid generator and a photoresist composition each comprising same, wherein the compound has excellent absorbance for light of i-line (365 nm) wavelength, is greatly easy to prepare into a polymerizable composition due to very high solubility in an organic solvent, has good thermal stability, and shows a favorable acid generation rate.

Inventors

• Chun Rim Oh
• Dae Hyuk CHOI
• Yu Na CHOI
• Deuk Rak LEE
• Ji Eun CHOI
• Ki Tae Kang
• Min Jung Kim
• Won Jung LEE
• Chi Wan LEE

Assignees

• SAMYANG CORPORATION

Dates

Publication Date

20260512

Application Date

20211228

Priority Date

20201228

Claims (11)

1. 1 . A sulfonic acid derivative compound of naphthalimide represented by the following Formula I: wherein R 1 and R 2 are each independently 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; and R 3 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 formula R 4 —O—(CH 2 ) n —, where n is an integer of 1 to 12 and R 4 is a substituted or unsubstituted aliphatic hydrocarbon group.
2. 2 . The sulfonic acid derivative compound of naphthalimide according to claim 1 , wherein R 1 and R 2 are each independently 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; and 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.
3. 3 . The sulfonic acid derivative compound of naphthalimide according to claim 1 , wherein R 1 and R 2 are each independently a C 1 -C 12 linear alkyl group or C 3 -C 12 branched alkyl group which is unsubstituted or substituted with one or more halogen atoms or alicyclic hydrocarbon groups; a C 3 -C 12 alicyclic hydrocarbon group which is unsubstituted or substituted with one or more halogen atoms; a C 6 -C 20 aryl group which is unsubstituted or substituted with one or more halogen atoms; a C 7 -C 20 arylalkyl group which is unsubstituted or substituted with one or more halogen atoms or C 1 -C 12 alkylthio groups; or a C 7 -C 20 alkylaryl group which is unsubstituted or substituted with one or more halogen atoms; and R 3 is a C 1 -C 12 linear alkyl group or C 3 -C 12 branched alkyl group which is unsubstituted or substituted with one or more halogen atoms or alicyclic hydrocarbon groups; a C 3 -C 12 alicyclic hydrocarbon group which is unsubstituted or substituted with one or more halogen atoms; a C 6 -C 20 aryl group which is unsubstituted or substituted with one or more halogen atoms; a C 7 -C 20 arylalkyl group which is unsubstituted or substituted with one or more halogen atoms or C 1 -C 12 alkylthio groups; a C 7 -C 20 alkylaryl group which is unsubstituted or substituted with one or more halogen atoms; or a C 1 -C 12 alkoxy-C 1 -C 4 alkyl group which is unsubstituted or substituted with one or more halogen atoms.
4. 4 . The sulfonic acid derivative compound of naphthalimide according to claim 1 , wherein R 1 is methyl group, ethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, nonafluorobutyl group or tosyl group; R 2 is methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, octyl group or cyclohexyl group; and R 3 is methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, heptyl group, cyclohexyl group, methoxyethyl group (CH 3 —O—CH 2 CH 2 —) or butoxyethyl group (CH 3 CH 2 CH 2 CH 2 —O—CH 2 CH 2 —).
5. 5 . The sulfonic acid derivative compound of naphthalimide according to claim 1 , which is selected from the following compounds:
6. 6 . A photoacid generator comprising a sulfonic acid derivative compound of naphthalimide according to claim 1 .
7. 7 . A photoresist composition comprising a sulfonic acid derivative compound of naphthalimide according to claim 1 ; and a binder resin.
8. 8 . A substrate coated with a photoresist composition according to claim 7 .
9. 9 . A patterned substrate obtained by exposing and developing a coated substrate according to claim 8 .
10. 10 . A display device comprising a patterned substrate according to claim 9 .
11. 11 . A semiconductor device comprising a patterned substrate according to claim 9 .

Description

TECHNICAL FIELD The present invention relates to a sulfonic acid derivative of naphthalimide, and a photoacid generator and a photoresist composition comprising the same, and more specifically, it relates to a sulfonic acid derivative of naphthalimide which has an excellent absorbance of light with i-line wavelength (365 nm), has a high solubility in an organic solvent so that a polymeric composition may be prepared easily, 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. 10-2012-0114353 disclose preparation of naphthalimide compound by using bromine-substituted compound. PROBLEMS TO BE SOLVED The purpose of the present invention is to provide a sulfonic acid derivative compound of naphthalimide which has an excellent photosensitivity suitable as photoacid generator used for photolithography 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 P t aspect of the present invention provides a sulfonic acid derivative compound of naphthalimide represented by the following Formula I: whereinR1 and R2 are each independently 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; andR3 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 formula R4—O—(CH2)n—, where n is an integer of 1 to 12 and R4 is a substituted or unsubstituted aliphatic hydrocarbon group.The 2nd aspect of the present invention provides a photoacid generator comprising the sulfonic acid derivative compound of naphthalimide according to the present invention.The 3rd aspect of the present invention provides a photoresist composition comprising the sulfonic acid derivative compound of naphthalimide according to the present invention; and a binder resin.Other aspects of the present invention provide a substrate coated with the photoresist composition according to 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 The sulfonic acid derivative compound of naphthalimide according to 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 generator in exposure and post-bake processes, and so it can reduce pollution and has the adva