KR101796993B1 - Fluorene derivatives, photopolymerization initiator and photoresist composition containing the same - Google Patents

Fluorene derivatives, photopolymerization initiator and photoresist composition containing the same Download PDF

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KR101796993B1
KR101796993B1 KR1020150118583A KR20150118583A KR101796993B1 KR 101796993 B1 KR101796993 B1 KR 101796993B1 KR 1020150118583 A KR1020150118583 A KR 1020150118583A KR 20150118583 A KR20150118583 A KR 20150118583A KR 101796993 B1 KR101796993 B1 KR 101796993B1
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alkyl
heterocycloalkyl
heteroaryl
cycloalkyl
aryl
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KR20170023448A (en
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김성현
김상하
허윤희
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(주)켐이
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Priority to CN201680057011.0A priority patent/CN108137443B/en
Priority to PCT/KR2016/008451 priority patent/WO2017023067A2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
    • C07C13/567—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered with a fluorene or hydrogenated fluorene ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/72—Spiro hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/20—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated
    • C07C219/22—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

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  • Physics & Mathematics (AREA)
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Abstract

The present invention relates to a novel fluorene derivative, a photopolymerization initiator comprising the same, and a photoresist composition, wherein the fluorene derivative according to the present invention has at least one unsaturated substituent group selected from the 9th and 10th positions of fluorene It is possible to provide a photopolymerization initiator and a photoresist composition capable of realizing high sensitivity in a wide range of absorption spectra.

Description

FIELD OF THE INVENTION The present invention relates to a fluorene derivative, a photopolymerization initiator and a photoresist composition containing the same,

The present invention relates to a fluorene derivative, a photopolymerization initiator and a photoresist composition containing the same, and more particularly to a novel fluorene derivative containing at least one unsaturated substituent selected from the 9th and 10th positions, a photopolymerization initiator Initiators and photoresist compositions.

The photopolymerization initiator is used in a photocurable ink, a photosensitive printing plate, various photoresists and the like because it can be selectively cured by irradiated light to form various patterns. As the photopolymerization initiator having such characteristics, various compounds such as acetophenone derivatives, benzophenone derivatives, bimidazole derivatives, acylphosphine oxide derivatives, triazine derivatives, and oxime derivatives are known. Among them, Patent Documents 1 to 3 disclose oxime ester compounds containing a carbazole skeleton, and Patent Document 4 discloses benzophenone derivatives. In the case of forming a pattern using such a conventional photopolymerization initiator, sensitivity of the photopolymerization initiator is lowered and the amount of photopolymerization initiator used is increased or the amount of exposure is increased. As a result, the photopolymerization initiator is decomposed And the yield is lowered due to the byproducts generated thereby, which is an obstacle to the improvement of productivity. Therefore, there is a demand for continuous research on a new photopolymerization initiator capable of meeting the needs of industrial sites and cost reduction effects by having properties such as high sensitivity, excellent thermal stability and storage stability.

Accordingly, Applicants have developed a novel fluorene derivative containing a specific unsaturated group having a significantly improved sensitivity and capable of realizing a high reaction conversion rate and having excellent thermal stability and solubility, and by using it, A photopolymerization initiator having high sensitivity and a photoresist composition containing the same.

1) Japanese Laid-Open Patent No. 2006-036750 2) International Patent Publication No. WO2002-100903 3) International Patent Publication No. WO2011-152066 4) United States Patent No. 4590145

An object of the present invention is to provide a novel fluorene derivative excellent in high sensitivity, heat resistance and chemical resistance, and a photopolymerization initiator and photoresist composition capable of realizing excellent physical properties such as residual film ratio and developability.

An object of the present invention is to provide a novel fluorene derivative represented by the following general formula (1).

[Chemical Formula 1]

Figure 112015081617890-pat00001

In the formula (1)

R 1 to R 8 are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C 6 -C 30) C3-C30) heteroaryl, amino (-NH 2), nitro (-NO 2), cyano (-CN), -OR 21, -SR 21, -OC (= 0) R 21, -C (= O ) R < 21 >, -C (= O) OR < 22 &

Figure 112015081617890-pat00002
, And at least one of R 1 to R 8 is
Figure 112015081617890-pat00003
And, n is an integer of 0 or 1, R 21 to R 24 are each independently (C1-C30) alkyl, (C3-C30) cycloalkyl (C1-C30) alkyl, (C3-C30) cycloalkyl, ( C3-C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl, -OR 31, -SR 31, -C (= O) R 31, -C (= O) OR 32, - NR 31 R 32 or -P (= O) (OR 32 ) (OR 33 ), wherein R 31 to R 33 are each independently hydrogen, deuterium, halogen, (C 1 -C 30) C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl;

R 9 and R 10 are each independently (C1-C30) alkyl, (C2-C30) is an alkenyl or (C2-C30) alkynyl seen, the R 9 and R 10 are connected to each other to form, or a single bond to the ring, (C 1 -C 5) alkylene, (C 2 -C 5) alkenylene, (C 2 -C 5) alkynylene, (C 6 -C 12) arylene or -Y 1 -Z 1 -Y 2 - And Y < 1 > Y 2 is each independently (C 1 -C 5) alkylene, Z 1 is (C 6 -C 12) arylene, and R 9 or R 10 comprises at least one unsaturated group;

Wherein R 1 to the R 8 alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl and wherein R 21 to the R 24 alkyl, cycloalkylalkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl and wherein R 9 and R 10 and R 9 and R 10 are independently selected from the group consisting of (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl, (C 3 -C 30) cycloalkyl, C3-C30) heterocycloalkyl, halogen, cyano, nitro, -CR d, -OR a, -SR a, -NR b R c, -C (= O) R a, -C (= O) OR a , -C (= O) NR b R c and P (= O) (OR a ) (OR b ), wherein n is an integer of 0 or 1, The R a and R b And R c are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl, (C 3 -C 30) cycloalkyl (C 1 -C 30) (C6-C30) aryl or (C3-C30) heteroaryl, wherein Rd is halogen and said heterocycloalkyl and heteroaryl are selected from the group consisting of B, N, O, S , P (= O), Si and P.

Another object of the present invention is to provide a photopolymerization initiator and a photoresist composition comprising at least one selected from the fluorene derivatives represented by the general formula (1).

Another object of the present invention is to provide a color filter or black matrix comprising the photoresist composition.

The fluorene derivative according to the present invention has a structure containing one or two selected unsaturated groups at positions 9 and 10 of the fluorene skeleton, and thus has not only high photosensitivity but also high solubility and excellent transparency .

By irradiating the photoresist composition containing the fluorene derivative according to the present invention with light, the rate of polymerization and curing reaction of the polymerizable compound having an unsaturated bond can be remarkably improved, and excellent reactivity can be realized even at a low exposure dose A black matrix, a color filter, a column spacer, an organic insulating film, a photoresist composition for an overcoat, and the like.

When a fluorene derivative having one or two unsaturated groups selected from the 9th and 10th positions of the skeleton according to the present invention is used as a photopolymerization initiator, desired physical properties can be realized even at a small amount due to high sensitivity But also the physical properties such as residual film ratio, chemical resistance and developability can be remarkably improved by reaction with a photosensitizer containing a thiol group, and it can be produced from a photopolymerization initiator in an exposure and post-baking process due to high thermal stability Out gas combustion can be minimized and the defect rate can be minimized.

The novel fluorene derivative, the photopolymerization initiator and the photoresist composition containing the novel fluorene derivative according to the present invention will be described below. However, unless otherwise defined in the technical terms and scientific terms used herein, And a description of known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted in the following description.

In order to achieve the object of the present invention, one or both of the selected unsaturated groups at the 9th and 10th positions of the fluorene may have a higher optical sensitivity. In one embodiment of the present invention, the basic skeleton of the fluorene derivative containing the specific unsaturated group may be represented by the following general formula (1).

[Chemical Formula 1]

Figure 112015081617890-pat00004

In the formula (1)

R 1 to R 8 are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C 6 -C 30) C3-C30) heteroaryl, amino (-NH 2), nitro (-NO 2), cyano (-CN), -OR 21, -SR 21, -OC (= 0) R 21, -C (= O ) R < 21 >, -C (= O) OR < 22 &

Figure 112015081617890-pat00005
, And at least one of R 1 to R 8 is
Figure 112015081617890-pat00006
And, n is an integer of 0 or 1, R 21 to R 24 are each independently (C1-C30) alkyl, (C3-C30) cycloalkyl (C1-C30) alkyl, (C3-C30) cycloalkyl, ( C3-C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl, -OR 31, -SR 31, -C (= O) R 31, -C (= O) OR 32, - NR 31 R 32 or -P (= O) (OR 32 ) (OR 33 ), wherein R 31 to R 33 are each independently hydrogen, deuterium, halogen, (C 1 -C 30) C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl;

R 9 and R 10 are each independently (C1-C30) alkyl, (C2-C30) is an alkenyl or (C2-C30) alkynyl seen, the R 9 and R 10 are connected to each other to form, or a single bond to the ring, (C 1 -C 5) alkylene, (C 2 -C 5) alkenylene, (C 2 -C 5) alkynylene, (C 6 -C 12) arylene or -Y 1 -Z 1 -Y 2 - And Y < 1 > Y 2 is each independently (C 1 -C 5) alkylene, Z 1 is (C 6 -C 12) arylene, and R 9 or R 10 comprises at least one unsaturated group;

Wherein R 1 to the R 8 alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl and wherein R 21 to the R 24 alkyl, cycloalkylalkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl and wherein R 9 and R 10 and R 9 and R 10 are independently selected from the group consisting of (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl, (C 3 -C 30) cycloalkyl, C3-C30) heterocycloalkyl, halogen, cyano, nitro, -CR d, -OR a, -SR a, -NR b R c, -C (= O) R a, -C (= O) OR a , -C (= O) NR b R c and P (= O) (OR a ) (OR b ), wherein n is an integer of 0 or 1, The R a and R b And R c are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl, (C 3 -C 30) cycloalkyl (C 1 -C 30) (C6-C30) aryl or (C3-C30) heteroaryl, wherein Rd is halogen and said heterocycloalkyl and heteroaryl are selected from the group consisting of B, N, O, S , P (= O), Si and P.

The term "halogen" of the present invention means fluoro, chloro, bromo or iodo.

All substituents, including the term "alkyl", and other "alkyl" part of the present invention to mean a hydrocarbon radical containing both a straight or branched chain type, and specific examples of methyl, ethyl, n - propyl, i - propyl, n -butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, n-hexyl, i-hexyl, s-hexyl, n- heptyl, n- octyl, n- nonyl , n-decyl, i -decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl.

In addition, the term "alkenyl" means an unsaturated hydrocarbon radical in the form of a straight chain or a branched chain containing at least one double bond, and specific examples thereof include ethenyl, prop-1-en-1-yl, 2-yl, prop-2-en-1-yl, 1-yl, but-2-en-1-yl, but-2-en-2-yl, buta- Dien-2-yl, and the like. The term "alkynyl" means an unsaturated hydrocarbon radical in the form of a straight or branched chain containing at least one triple bond. Specific examples thereof include ethynyl, prop- 1-yl, prop-2-yn-1-yl, but-1-yn-1-yl, It is not.

The term "cycloalkyl ", as used herein, may refer to fully saturated and partially unsaturated hydrocarbon rings of from 3 to 9 carbon atoms, including those where aryl or heteroaryl is fused. The term "heterocycloalkyl" can also be a monocyclic or polycyclic non-aromatic radical comprising at least one heteroatom selected from B, N, O, S, P (= O), Si and P.

The term "aryl " of the present invention is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, which may be monocyclic or polycyclic aromatic hydrocarbon radicals, suitably containing from 3 to 7, Includes a single or fused ring system containing 5 or 6 ring atoms and includes a form in which a plurality of aryls are connected by a single bond, and specific examples thereof include phenyl, naphthyl, biphenyl, terphenyl, anthryl, But are not limited to, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, crycenyl, naphthacenyl, fluoranthenyl and the like.

The term "heteroaryl ", as used herein, refers to an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, such as 3, including at least one heteroatom selected from B, N, O, S, P To 8 ring atoms, and includes a single or fused ring system, suitably containing from 3 to 7, preferably 5 or 6, ring atoms in each ring And includes a form in which a plurality of heteroaryls are connected by a single bond. Specific examples include furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, Monocyclic heteroaryl such as isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl; And benzofuranyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazole Polycyclic heteroaryl such as benzyl, tolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinolizinyl, quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl and the like; But the present invention is not limited thereto.

R 9 and R 10 may form a ring by connecting an alkylene or an alkenylene which is unsubstituted or substituted by methylene,

Figure 112015081617890-pat00007
,
Figure 112015081617890-pat00008
,
Figure 112015081617890-pat00009
,
Figure 112015081617890-pat00010
,
Figure 112015081617890-pat00011
,
Figure 112015081617890-pat00012
,
Figure 112015081617890-pat00013
,
Figure 112015081617890-pat00014
or
Figure 112015081617890-pat00015
A connector as exemplified by; And a linking group substituted with one or more methylene groups in the linking group; May be used to form a ring, but the present invention is not limited thereto.

The compound represented by the formula (1) according to an embodiment of the present invention has a high solubility in a solvent and a high sensitivity in a wide range of absorption spectra, and R 9 and R 10 are each independently (C 1 -C 10) alkyl, (C2-C10) alkenyl or (C2-C10) alkynyl, and wherein R 9 and R 10 are optionally substituted with a methylene (C1-C5) alkylene or (C2-C5) alkenylene each other (C 1 -C 5) alkenylene, (C 2 -C 5) alkynylene, (C 6 -C 12) arylene or -Y 1 -Z 1 -Y 2 < - >, and Y < 1 > and Y < Y 2 are each independently a (C1-C5) alkylene, wherein Z 1 is (C6-C12) arylene, and, or (C6-C12) aryl alkylene, wherein R 9 or R 10 is more surely one kinds of unsaturated But is not limited thereto.

It has been confirmed that the fluorene derivative according to an embodiment of the present invention can significantly improve the sensitivity to light by containing at least one oxime ester group at a specific position. Further, by containing at least one unsaturated group selected from the 9th and 10th positions of the fluorene, the adhesion to the substrate and the ability to form a fine pattern are improved by reacting with the photosensitizer containing a thiol group, and the sensitivity, And the like can be optimized.

Preferably, the fluorene derivative has high solubility and is excellent in compatibility with additives such as various binder resins, pigments and photo-sensitizers added to the photoresist composition, and has high thermal stability, so that exposure and post-baking processes May be a fluorene derivative represented by the following general formula (2) or (3), but the present invention is not limited thereto.

(2)

Figure 112015081617890-pat00016

In the formula (2)

R 1 , R 3 to R 6 and R 8 are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, -C30) aryl, (C3-C30) heteroaryl, amino (-NH 2), nitro (-NO 2), cyano (-CN), -OR 21, -SR 21, -OC (= 0) R 21 , -C (= O) R 21 , -C (= O) OR 22 or

Figure 112015081617890-pat00017
, And at least one of R 1 to R 8 is
Figure 112015081617890-pat00018
And, n is an integer of 0 or 1, R 21 to R 24 are each independently (C1-C30) alkyl, (C3-C30) cycloalkyl (C1-C30) alkyl, (C3-C30) cycloalkyl, ( C3-C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl, -OR 31, -SR 31, -C (= O) R 31, -C (= O) OR 32, - NR 31 R 32 or -P (= O) (OR 32 ) (OR 33 ), wherein R 31 to R 33 are each independently hydrogen, deuterium, halogen, (C 1 -C 30) C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl;

R 9 and R 10 are each independently (C1-C30) alkyl, (C2-C30) is an alkenyl or (C2-C30) alkynyl seen, the R 9 and R 10 are connected to each other to form, or a single bond to the ring, (C 1 -C 5) alkylene, (C 2 -C 5) alkenylene, (C 2 -C 5) alkynylene, (C 6 -C 12) arylene or -Y 1 -Z 1 -Y 2 - And Y < 1 > Y 2 is each independently (C 1 -C 5) alkylene, Z 1 is (C 6 -C 12) arylene, and R 9 or R 10 comprises at least one unsaturated group;

R 21 , R 23 and R 24 are each independently selected from the group consisting of (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl, -OR 31, -SR 31, -C (= O) R 31, -C (= O) oR 32, -NR 31 R 32 or -P ( = O) (OR 32 ) (OR 33 ), wherein R 31 to R 33 are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 3 -C 30) C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl;

n and m are each independently an integer of 0 or 1;

The alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R 1 , R 3 to R 6 and R 8 and the alkyl, cycloalkylalkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R 21 to R 24 , and wherein R 9 and R 10 alkyl, alkenyl, alkynyl, and R 9 and R 10 is a ring formed are connected to each other are each independently (C1-C30) alkyl, (C2-C30) alkenyl, (C3-C30 ) cycloalkyl, (C3-C30) heterocycloalkyl, halogen, cyano, nitro, -CR d, -OR a, -SR a, -NR b R c, -C (= O) R a, -C ( = O) OR a , -C (= O) NR b R c and P (= O) (OR a ) (OR b ) Each independently represents an integer of 0 or 1, and R a , R b And R c are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl, (C 3 -C 30) cycloalkyl (C 1 -C 30) (C6-C30) aryl or (C3-C30) heteroaryl, wherein Rd is halogen and said heterocycloalkyl and heteroaryl are selected from the group consisting of B, N, O, S , P (= O), Si and P.

(3)

Figure 112015081617890-pat00019

In Formula 3,

R 1 , R 3 to R 6 and R 8 are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, -C30) aryl, (C3-C30) heteroaryl, amino (-NH 2), nitro (-NO 2), cyano (-CN), -OR 21, -SR 21, -OC (= 0) R 21 , -C (= O) R 21 , -C (= O) OR 22 or

Figure 112015081617890-pat00020
, And at least one of R 1 to R 8 is
Figure 112015081617890-pat00021
And, n is an integer of 0 or 1, R 21 to R 24 are each independently (C1-C30) alkyl, (C3-C30) cycloalkyl (C1-C30) alkyl, (C3-C30) cycloalkyl, ( C3-C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl, -OR 31, -SR 31, -C (= O) R 31, -C (= O) OR 32, - NR 31 R 32 or -P (= O) (OR 32 ) (OR 33 ), wherein R 31 to R 33 are each independently hydrogen, deuterium, halogen, (C 1 -C 30) C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl;

R 9 is (C1-C30) alkyl, (C2-C30) alkenyl or (C2-C30) alkynyl;

M is a single bond, (C1-C5) alkylene, (C2-C5) alkenylene, (C2-C5) alkynylene, (C6-C12) arylene or -Y 1 -Z 1 -Y 2 - is connected to the dimer Lt; RTI ID = 0.0 > Y1 < / RTI > and Y 2 is each independently (C 1 -C 5) alkylene, Z 1 is (C 6 -C 12) arylene, and R 9 or M contains at least one unsaturated group;

R 21 , R 23 and R 24 are each independently selected from the group consisting of (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl, -OR 31, -SR 31, -C (= O) R 31, -C (= O) oR 32, -NR 31 R 32 or -P ( = O) (OR 32 ) (OR 33 ), wherein R 31 to R 33 are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 3 -C 30) C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl;

n and m are each independently an integer of 0 or 1;

The alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R 1 , R 3 to R 6 and R 8 and the alkyl, cycloalkylalkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R 21 to R 24 , and wherein R 9 and R 10 alkyl, alkenyl, alkynyl, and R 9 and R 10 is a ring formed are connected to each other are each independently (C1-C30) alkyl, (C2-C30) alkenyl, (C3-C30 ) cycloalkyl, (C3-C30) heterocycloalkyl, halogen, cyano, nitro, -CR d, -OR a, -SR a, -NR b R c, -C (= O) R a, -C ( = O) OR a , -C (= O) NR b R c and P (= O) (OR a ) (OR b ) Each independently represents an integer of 0 or 1, and R a , R b And R c are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl, (C 3 -C 30) cycloalkyl (C 1 -C 30) (C6-C30) aryl or (C3-C30) heteroaryl, wherein Rd is halogen and said heterocycloalkyl and heteroaryl are selected from the group consisting of B, N, O, S , P (= O), Si and P.

In the case of the fluorene derivative represented by the above formula (2) or (3) according to the present invention, R 9 and R 10 are each independently selected from the group consisting of C1 -C10) alkyl, (C2-C10) alkenyl or (C2-C10) alkynyl, and R 2 of formula 9, and R 10 is (C1-C5) alkylene or (C2- optionally substituted with methylene C5) alkenylene, (C2-C5) alkenylene, (C2-C5) alkynylene, (C2-C5) alkenylene, C6-C12) arylene or -Y 1 -Z 1 -Y 2 - may form a dimer linked, the Y 1 and Y 2 is each independently (C 1 -C 5) alkylene, and Z 1 is (C 6 -C 12) arylene and (C 2 -C 5) alkenylene.

The fluorene derivative represented by the formula (1) according to an embodiment of the present invention has a high solubility as well as a high sensitivity in view of improving the physical properties such as the desired residual film ratio, chemical resistance and developability even in a small amount Structure, but is not limited thereto.

Figure 112015081617890-pat00022

Figure 112015081617890-pat00023

Figure 112015081617890-pat00024

Figure 112015081617890-pat00025

The fluorene derivative according to the present invention can be prepared by the method shown in the following Reaction Schemes 1 to 5 and can be prepared by various synthetic methods.

[Reaction Scheme 1]

Figure 112015081617890-pat00026

[Reaction Scheme 2]

Figure 112015081617890-pat00027

[Reaction Scheme 3]

Figure 112015081617890-pat00028

[Reaction Scheme 4]

Figure 112015081617890-pat00029

[Reaction Scheme 5]

Figure 112015081617890-pat00030

[Reaction schemes 1 to 5]

The definition of the substituent is as defined in Chemical Formula 1.]

The fluorene derivative according to the present invention can be prepared by introducing an oxime ester at a position 2, which is a photoactive compound having a high UV light absorption rate, and by changing a substituent at the side chain and substituents at positions 9 and 10, It can be applied to various purposes by adjusting pattern properties and adjusting the physical properties of thin films such as heat resistance and chemical resistance.

The present invention provides a photopolymerization initiator comprising the fluorene derivative.

The present invention also provides a photoresist composition comprising the fluorene derivative.

The photoresist composition according to the present invention includes a binder resin, a colorant, and a fluorene derivative. The fluorene derivative may be contained in an amount of 0.01 to 15% by weight based on 100% by weight of the entire photoresist composition, 10% by weight, and more preferably 0.01% by weight to 5% by weight, may minimize contamination by by-products decomposed after photoinitiation.

The binder resin is not limited if it is known in the art, but it has an average molecular weight of from 2,000 to 300, 000 g / mol and a dispersion degree of from 1.0 to 10.0 in terms of high compatibility with the fluorene derivative according to the present invention Acrylic polymer, novolak resin, and the like. The acrylic polymer may be a copolymer of monomers containing the following monomers. Specific examples of the monomer include, but not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (Meth) acrylate, dodecyl (meth) acrylate, isooctyl (meth) acrylate, isooctyl (meth) acrylate, (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (Meth) acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid anhydride, maleic acid monoalkyl ester, monoalkyl itaconate, monoalkyl fumarate, glycidyl acrylate (Meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (Meth) acrylate, styrene,? -Methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, (Meth) acrylamide, N-methyl (meth) acrylamide, etc. These monomers may be used alone or in combination of two or more kinds thereof. The novolak resin is a phenolic compound and an aldehyde compound The phenolic compound is not particularly limited and specific examples thereof include phenol, o-, m-, and p-cresol, 2,5-xylenol, 3,4- Butylphenol, 4-t-butylphenol, 2-ethylphenol, 3-ethylphenol, 3-t- Butylphenol, 4-methyl-2-t-butylphenol, 2-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1 And 7-dihydroxynaphthalene. These may be one or a mixture of two or more of them. The aldehyde compound is not particularly limited, and specific examples thereof include formaldehyde, p-formaldehyde, acetaldehyde Propyl aldehyde,? - and? -Phenyl propyl aldehyde, benzaldehyde, o-, m- and p-hydroxybenzaldehyde, o- and p-methylbenzaldehyde, glutaraldehyde, , Glycidyl, and the like can be mentioned the oxalate, these may be that the mixture of at least one or two, preferably benzyl (meth) acrylate and meth preferably a copolymer of acrylic acid.

The coloring material is not limited as long as it is known in the art, and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, Anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone pigments, anthraquinone pigments, anthraquinone pigments, anthanthrone pigments, anthanthrone pigments, anthanthrone pigments, indanthrone pigments, Pigments, diketopyrrolo pyrrole pigments, and the like. Specific examples of the inorganic pigment include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, Oxide, carbon black and the like. Particularly, the above organic pigments and inorganic pigments can be compounds classified as pigments in the color index (The Society of Dyers and Colourists), and more specific examples include C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264; C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76; C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58; C.I. Pigment Brown 28; C.I Pigment Black 1 and 7 pigments of a color index (C.I.) number, but are not limited thereto. The coloring material may be used in the form of a dispersion. Examples of the solvent for forming the coloring material dispersion include ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl Ether, propylene glycol monomethyl ether acetate, propylene glycol methyl ether propionate, and the like. The colorant dispersion may be prepared by mixing 0.1 to 30% by weight of the solid content colorant based on 100% by weight of the total weight of the colorant dispersion.

The photoresist composition according to the present invention may further comprise a photosensitizer. At this time, the photosensitizer preferably contains a thiol group, and the photosensitizer containing a thiol group can rapidly react with the fluorene derivative according to the present invention to realize sensitivity to the remarkably enhanced light, The residual film ratio and developability of the produced color filter, black matrix and the like can be significantly improved.

The photosensitizer having high reactivity with the fluorene derivative according to the present invention is not limited as long as it contains a thiol group, and examples thereof include pentaerythritol tetrakis thioglycolate, pentaerythritol tetrakisthiophene But may be at least one selected from pentaerythritol tetrakis thiopropionate and pentaerythritol tetrakis (3-mercapto butylate). In addition, when the photoresist composition is mixed in an amount of 0.01 to 10% by weight based on 100% by weight of the photoresist composition, optimal sensitivity can be achieved due to reaction with the fluorene derivative according to the present invention.

The photoresist composition according to the present invention may further contain at least one additional additive selected from solvents, adhesion aids, thermal polymerization inhibitors, leveling agents, antifoaming agents, and the like other than the photosensitizer containing the colorant, the fluorene derivative, the binder resin and the thiol group .

As the solvent, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl (meth) acrylate and the like are added in consideration of compatibility with the binder resin, the photopolymerization initiator according to the present invention, Propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl lactate, ethyl lactate, Diethyleneglycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl (NMP),? -Butyrolactone, diethyl ether, ethylene glycol dimethyl ether, Diglyme, The solvent may be selected from the group consisting of tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, , Heptane, and octane may be used alone or in combination of two or more, but the present invention is not limited thereto.

The adhesion promoter may be a silicone compound having an epoxy group or an amine group, but is not limited thereto. Specific examples thereof include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) dimethyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, , 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl ) Ethyltriethoxysilane, 2-methacryloxypropyltrimethoxysilane, and aminopropyltrimethoxysilane, which may be used alone or in combination of two or more.

Further, as additional additives commonly used in the art, hydroquinone, hydroquinone having a substituent such as an alkyl ether, catechol having a substituent such as an alkyl ether such as butyl catechol, pyrogallol, 2,2,6, A radical chelating agent such as 6-tetramethyl-1-piperidinyloxy radical, at least one heat polymerization inhibitor selected from thiophenols,? -Naphthyl amines and? -Naphthols; BM-1000 and BM-1100 from BM Chemie. Mechac-packs F 142D, F 172, F 173, and F 183 manufactured by Dainippon Ink & Chemicals Incorporated. Prorad FC-135, FC-170C, FC-430, FC-431 of Sumitomo Heavy Industries, S-112, S-113, S-131, S-141 and S-145 of Saffron copper of Asahi Glass Co., SH-28PA, Dong-190, Dong-93, SZ-6032 and SF-8428 of Toray Silicone Co., A leveling agent of a commercially available product, etc. may be further mixed and used, but the present invention is not limited thereto.

The photoresist composition according to the present invention contains at least one fluorene derivative represented by the above Chemical Formulas 1 and 2 having high photoactivity, thereby providing a color filter excellent in developing property, durability and chemical resistance with high brightness and high contrast ratio Can be implemented.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are illustrative of the present invention but are not limited thereto. All of the following compound examples were run in an inert argon or nitrogen atmosphere using a glove box or Schlenk line and the product was analyzed using 1 H Nuclear Magnetic Resonance (NMR).

Preparation of acetate (1) (Example 1) 1- (9,9-diallyl -9 H-fluoren-2-yl) -1,2-propane-dione-2-oxime-O

Step 1. Preparation of fluorene-9,9-diallyl -9 H

27.0 g (481.29 mmol) of potassium hydroxide and 1.99 g (12.03 mmol) of potassium iodide were dissolved in 140 ml of anhydrous tetrahydrofuran under nitrogen atmosphere and maintained at 15 ° C. Then, 30.57 g of allyl bromide 252.67 mmol) was diluted with 40 ml of anhydrous tetrahydrofuran and slowly added dropwise. After the dropwise addition, the mixture was stirred at room temperature (23 ° C) for 1 hour. After pouring slowly into 300 ml of ice distilled water, the reaction was terminated and the product was extracted with 500 ml of dichloromethane. The organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain the product (solvent: ethyl Oh glyphosate acid: n-hexane = 1: 15) of liquid 9,9-purified light yellow viscous to as diallyl -9 H - FLOUR 29.64 g (yield: 84%) of an orange was obtained.

1 H-NMR (δ ppm: CDCl 3): 3.52-3.64 (4H, d), 5.09-5.28 (4H, m), 6.0 ~ 6.18 (2H, m), 7.24-7.35 (4H, m), 7.41- 7.56 (2H, d), 7.73 (2H, d)

Step 2. Preparation of 1- (9,9-diallyl -9 H-fluoren-2-yl) - propan-1-one prepared

The 9,9-diallyl -9 H prepared as described in Step 1-fluorene 10.0g (40.59mmol) was stirred and dissolved in 70ml of dichloromethane was cooled to 0 ℃ in a nitrogen atmosphere. After cooling, 5.46 g (48.71 mmol) of aluminum chloride was slowly added thereto, followed by stirring for 30 minutes. 4.50 g (48.71 mmol) of propionyl chloride was diluted with 20 ml of dichloromethane, and the mixture was slowly added dropwise, followed by stirring at 0 ° C for 1 hour. The reaction was warmed to room temperature, stirred for 4 hours and then re-cooled to 0 ° C. After cooling, the reaction was terminated by slowly pouring into 200 ml of ice-distilled water. The organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain the product (solvent: ethyl Oh glyphosate acid: n-hexane = 1: 8) to give a pale yellow solid of 1- (9,9-diallyl -9 H - FLOUR Yl-propan-1-one (yield: 58%).

1 H-NMR (δ ppm: CDCl 3): 1.22 (3H, t), 3.01 (2H, q), 3.55-3.68 (4H, d), 5.18-5.33 (4H, m), 6.10-6.27 (2H, m), 7.34-7.49 (3H, m), 7.70-7.87 (2H, d), 7.95-8.05

Step 3. Preparation of 1- (9,9-diallyl -9 H - fluoren-2-yl) -1,2-propane-dione-2-oxime prepared

The 1-prepared in Step 2 (9,9-diallyl -9 H-fluoren-2-yl) - propan-1-one 10.0g (33.06mmol) was dissolved in 60ml of tetrahydrofuran in a nitrogen atmosphere 20 ml of 4N hydrogen chloride (1,4-dioxane) and 4.65 g (39.68 mmol) of isopentyl nitrite were added. And the mixture was stirred at room temperature for 4 hours. The reaction was poured slowly into 150 ml of distilled water and the reaction was terminated. The solid precipitate was filtered, dissolved in ethyl acetate, and washed sequentially with saturated sodium hydrogencarbonate and distilled water. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. After concentration under reduced pressure the filtrate was light yellow solid 1- (9,9-diallyl -9 H - fluoren-2-yl) -1,2-propane-dione-2-oxime to give a 8.32g (76%).

1 H-NMR (? Ppm: CDCl 3 ): 2.27 (3H, s), 3.54-3.69 (4H, d), 5.20-5.36 (4H, m), 6.11-6.22 3H, m), 7.72-7.85 (2H, d), 7.97-8.06 (2H, d), 8.23

Step 4. Preparation of 1- (9,9-diallyl -9 H - fluoren-2-yl) -1,2-propane-dione-2-oxime - O - acetate (1) Preparation

The 1-prepared in step 3 (9,9-diallyl -9 H - fluoren-2-yl) -1,2-propane-dione-2-oxime were dissolved in 5.0g (15.08mmol) in 30ml dichloromethane 2.31 g (22.63 mmol) of acetic anhydride was added. The reaction product was heated, stirred at 70 ° C for 2 hours, and cooled to room temperature. 20 ml of dichloromethane was added, and the mixture was washed successively with saturated sodium hydrogencarbonate and distilled water. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. After concentration under reduced pressure and the filtrate yellow liquid 1- (9,9-diallyl -9 H - fluoren-2-yl) -1,2-propane-dione-2-oxime - O - acetate 4.39g (78%) ≪ / RTI >

1 H-NMR (δ ppm: CDCl 3) 2.20 (3H, s), 2.35 (3H, s), 3.48-3.59 (4H, d), 5.17-5.32 (4H, m), 5.99-6.09 (2H, m ), 7.36-7.49 (3H, m), 7.76-7.87 (2H, d), 8.10-8.20 (2H,

(Example 2) 1 - (9- (3-methylene-cyclohexyl) -9 H - fluoren-2-yl) -1,2-propane-dione-2-oxime - O - acetate (4)

Step 1. 9- (3-cyclohexane turned on) -9 H - Preparation of fluorene

(61.36 mmol) of 1,5-dibromopentan-3-one were dissolved in 350 ml of anhydrous tetrahydrofuran under nitrogen atmosphere, and the temperature was maintained at 5 ° C. Then, 0.99 g of potassium iodide (6.01 mmol). 13.50 g (240.64 mmol) of potassium hydroxide was added in small portions while paying attention to heat generation. After the addition, the reaction mixture is heated to 15 DEG C and stirred for 1 hour and then stirred at room temperature for 1 hour. After pouring slowly into 500 ml of ice distilled water, the reaction was terminated and the product was extracted with 300 ml of dichloromethane. The organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure, and the obtained product was purified by silica gel column chromatography (solvent: ethyl acetate: n-hexane = 1: 20) to obtain pale yellow solid. 9- (3-cyclohexane turned on) -9 H - fluoren to obtain 4.33g (yield 29%).

1 H-NMR (? Ppm: CDCl 3 ): 2.29-2.47 (4H, t), 2.47-2.68 (4H, t), 7.25-7.37 (4H, m), 7.43-7.52 2H, d)

Step 2. 9- (3-methylene-cyclohexyl) -9 H - Preparation of fluorene

6.28 g (44.29 mmol) of methane iodide and 11.09 g (42.28 mmol) of triphenylphosphine were dissolved in 70 ml of anhydrous tetrahydrofuran under a nitrogen atmosphere, and the mixture was refluxed at 70 ° C for 4 hours. The reaction was cooled to room temperature and 4.97 g (44.29 mmol) of potassium tert-butoxide (t-BuOK) was diluted in 25 ml of tetrahydrofuran and added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Step 1 (3-on-cyclohexane), a 9-manufactured -9 H - fluorene 10.0g (40.27mmol) added and the tetrahydrofuran 40ml, and added slowly to reflux temperature and stirred at 70 ℃ for 4 hours. The mixture was cooled to room temperature, ethyl acetate and water were injected to separate the organic layer, and the washing with water was repeated twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure to a yellow solid of 9- (3-methylene-cyclohexyl) -9 H - fluorene was obtained 9.92g (82% yield).

1 H-NMR (δ ppm: CDCl 3): 2.15-2.32 (4H, t), 2.32-2.49 (4H, t), 4.82-4.99 (2H, m), 7.23-7.34 (4H, m), 7.40- 7.51 (2 H, d), 7.73 (2 H, d)

Step 3. Preparation of 1-acetate (9- (3-methylene-cyclohexyl) -9 H-fluoren-2-yl) -1,2-propane-dione-2-oxime-O

And are the same except for the use of fluorene-9,9-in Example 1 from step 2 of diallyl -9 H-fluorene in place of the prepared in Step 2 9- (3-methylene-cyclohexyl) -9 H method of example 1, step 2 to step 4 to perform a 1-of (-9 H 9- (3- methylene-cyclohexyl) - fluorene-2-yl) -1,2-propane-dione-2-oxime-O -Acetate (61%).

1 H-NMR (? Ppm: CDCl 3 ): 2.17 (3H, s), 2.18-2.31 (4H, t), 2.31-2.49 (7H, m), 4.88-5.02 (2H, m), 7.33-7.46 3H, m), 7.75-7.87 (2H, d), 8.11-8.20 (2H, d)

(Example 3) 1- (9- (2-cyclopentyl butenyl) -9 H - fluoren-2-yl) -1,2-propane-dione-2-oxime - O - acetate 6

Step 1 was carried out in the same manner as in Example 2 except that 1,4-dibromo-2-butene was used instead of 1,5-dibromopentan-3-one in the step 1 of Example 2 9- (2-cyclopentyl butenyl) -9 H-fluoren-manufactured and then, 9,9-diallyl in step 2 of example 1 -9 H-fluorene instead of 9- (2-cyclopentyl butenyl) - 9 H-fluoren except for the use of fluorene and performs the steps in example 1 step 2 to 4 in the same way to a pale yellow solid of 1- (9- (2-cyclopentyl butenyl) -9 H-fluorene- 3.18 g (66%) of 2-propyldione-2-oxindine- O -acetate was obtained

1 H-NMR (δ ppm: CDCl 3): 2.20 (3H, s), 2.34 (3H, s), 2.62-2.76 (4H, d), 5.71-5.82 (2H, d), 7.35-7.48 (3H, m), 7.76-7.88 (2H, d), 8.11-8.22 (2H, d)

(Example 4) 1- (9- (2-norbornene) methyl-9 H -9-methyl - fluoren-2-yl) -1,2-propane-dione-2-oxime - O - acetate (9 )

Preparation of fluorene-9-methyl-1 step -9 H

15.19 g (270.72 mmol) of potassium hydroxide and 0.89 g (5.41 mmol) of potassium iodide were dissolved in 200 ml of anhydrous tetrahydrofuran under nitrogen atmosphere and maintained at 15 DEG C. Then, 25.61 g 180.48 mmol) was diluted with 100 ml of anhydrous tetrahydrofuran and slowly added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. After pouring slowly into 400 ml of ice distilled water, the reaction was terminated and the product was extracted with 400 ml of dichloromethane. The organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain the product (solvent: ethyl Oh glyphosate acid: n-hexane = 1: 15) to give a yellow solid as a 9-methyl--9 H - fluorene 17.89g (Yield 55% ).

1 H-NMR (δ ppm: CDCl 3): 1.58 (3H, s), 4.6 (1H, q), 7.24-7.40 (4H, m), 7.40-7.49 (2H, d), 7.73 (2H, d)

Preparation of fluorene-Step 2. 9- (2-norbornene) -9-methyl-9-methyl-H

And to perform the step 1 in the same manner except for the use of methane iodide instead of 5-bromomethyl-norbornene in the above step 1 9- (2-norbornene) methyl-9 H -9-methyl - fluoren 8.89 g (yield: 68%) was obtained.

1 H-NMR (? Ppm: CDCl 3 ): 1.32-156 (2H, m), 1.58-1.70 (4H, m), 1.72-1.85 (2H, m), 2.20-2.29 (2H, d), 7.75 (2H, d), 7.21-7.40 (2H,

Of the acetate (9) Step 3. 1 - (9- (2-norbornene) -9-methyl-9-methyl-H-fluoren-2-yl) -1,2-propane-dione-2-oxime-O Produce

In the same manner except for the use of fluorene-9,9-in Example 1 from step 2 of diallyl -9 H-fluorene instead of 9- (2-norbornene) -9-methyl-9-methyl-H of example 1, step 2 to step 4 to perform a yellow solid 1-of (9- (2-norbornene) methyl-9 H -9-methyl - fluoren-2-yl) -1,2-propane (61%) of dione-2-oxime- O -acetate

1 H-NMR (δ ppm: CDCl 3): 1.31-1.68 (6H, m), 1.74-1.90 (2H, m), 2.20-2.30 (5H, m), 2.30-2.72 (5H, m), 6.34- 6.46 (2H, d), 7.40-7.52 (3H, m), 7.81-7.90 (2H, d), 8.24-8.36

(Example 5) 1- (9- (2-ethyl allyl phosphonium formate) -9 H -9-methyl - fluoren-2-yl) -1,2-propane-dione-2-oxime - O - acetate (10)

Step 1. Synthesis of 9- (2-bromoethyl) -9-methyl-9 H - Preparation of fluorene

Example 4 9-methyl-a prepared in Step 1-9 of the H - fluorene 15.0g (83.21mmol), anhydrous potassium hydroxide tetrahydro 7.0g (124.82mmol) of potassium iodide and 0.41g (2.49mmol) under a nitrogen atmosphere After dissolving in 150 ml of furan and keeping at 15 캜, 16.41 g (87.37 mmol) of 1,2-dibromoethane was diluted in 50 ml of anhydrous tetrahydrofuran and slowly added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. After pouring slowly into 300 ml of ice distilled water, the reaction was terminated and the product was extracted with 300 ml of dichloromethane. The organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure, and the obtained product was purified by silica gel column chromatography (solvent: ethyl acetate: n-hexane = 1: 15) to obtain a pale yellow liquid 9- (2-bromoethyl) -9 -methyl -9 H-fluorene 13.86g (yield 58%).

1 H-NMR (δ ppm: CDCl 3): 1.54 (3H, s), 2.41-2.50 (2H, t), 3.54-3.62 (2H, t), 7.26-7.41 (4H, m), 7.42-7.51 ( 2H, < / RTI > d), 7.75 (2H, d)

Step 2. 9- (2-ethyl allyl phosphonium formate) -9 H -9-methyl - Preparation of fluorene

7.68 g (132.31 mmol) of allyl alcohol and 13.39 g (132.31 mmol) of triethylamine were dissolved in 70 ml of anhydrous tetrahydrofuran under nitrogen atmosphere, and the temperature was maintained at 0 ° C. Then, 5.73 g (41.78 mmol) of phosphorus trichloride was dissolved in anhydrous tetrahydrofuran And the mixture was slowly added dropwise, followed by stirring at room temperature for 1 hour. The reaction product is separated into a precipitate and a filtrate using a filter paper. Was charged with fluorene 10.0g (34.82mmol) - was concentrated under reduced pressure and the filtrate was dissolved in 20ml dimethylacetamide and the 9- (2-bromoethyl) -9-methyl-9-H prepared as described in Step 1. The reaction was heated to 120 DEG C and refluxed and stirred for 12 hours. After pouring slowly into 100 ml of distilled water, the reaction was terminated and the product was extracted with 200 ml of dichloromethane. The organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure, and the obtained product was purified by silica gel column chromatography (solvent: ethyl acetate: n-hexane = 1: 8) to obtain a solid yellow 9- (2-diallylethylphosphorate) -9- methyl -9 H - fluorene was obtained 8.33g (65% yield).

1 H-NMR (δ ppm: CDCl 3): 1.49 (3H, s), 2.32-2.41 (2H, t), 2.81-2.92 (2H, t), 4.71-4.86 (4H, d), 5.62-5.74 ( 4H, m), 6.34-6.41 (2H, t), 7.24-7.39 (4H, m), 7.40-7.49

Step 3. 1 - (9- (2-ethyl allyl phosphonium formate) -9 H -9-methyl - fluoren-2-yl) -1,2-propane-dione-2-oxime - O - acetate (10 )

Except the use of a fluorene-the embodiment in the steps 1 2 9,9-diallyl -9 H-fluorene instead of 9- (2-ethyl-diallyl phosphonate formate) -9-methyl-9-H performing the steps of one embodiment 2 to step 4 in the same manner and the yellow solid 1- (9- (2-ethyl allyl phosphonium formate) -9 H -9-methyl - fluoren-2-yl) -1 , 2.08 g (52%) of 2-propanedione-2-oxime- O -acetate was obtained

1 H-NMR (δ ppm: CDCl 3): 1.48 (3H, s), 2.24 (3H, s), 2.34 (3H, s), 2.34-2.43 (2H, m), 2.82-2.93 (2H, t) , 4.70-4.84 (4H, d), 5.62-5.72 (4H, m), 6.32-6.40 (2H, t), 7.38-7.49 (3H, m), 7.78-7.90 (2H, d), 8.10-8.19 2H, d)

Preparation of butane (11) (Example 6) 1,4-bis (1-acetate (9-allyl -9 H - fluoren-9-yl) -1,2-propane-dione-2-oxime - - O)

Step 1. Synthesis of 1,4-bis (9-allyl -9 H - fluoren-9-yl) butane prepared in

The embodiment in the steps 41 but using allyl bromide instead of methane iodide is 9-allyl -9 H by performing the step 1 in Example 4 in the same manner was obtained fluorene. -9 H allyl prepared 9-fluorene 10.0g (48.47mmol), potassium hydroxide 5.44g (96.95mmol) of potassium iodide and 0.48g (2.90mmol) in 15 ℃ dissolved in 70ml of anhydrous tetrahydrofuran and under a nitrogen atmosphere , 5.23 g (24.23 mmol) of 1,4-dibromobutane was diluted with 20 ml of anhydrous tetrahydrofuran and slowly added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. After pouring slowly into 200 ml of ice distilled water, the reaction was terminated and the product was extracted with 300 ml of dichloromethane. The organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain the product (solvent: ethyl Oh glyphosate acid: n-hexane = 1: 4) to give a yellow solid of 1,4-bis (9-allyl -9 H - fluoren -9-yl) butane (yield: 64%).

1 H-NMR (? Ppm: CDCl 3 ): 1.41-1.55 (4H, t), 2.22-2.35 (4H, t), 3.52-3.72 (4H, m) M), 7.22-7.42 (8H, m), 7.42-7.64 (4H, m), 7.70-7.78 (4H, m)

Step 2. 1,4-bis (1- (9-allyl -9 H-fluoren-9-yl) - propan-1 is ON) butane

The 1,4-bis prepared in Step 1-a (9-allyl -9 H-fluoren-9-yl) butane 15.0g (32.14mmol) was stirred and dissolved in 120ml of dichloromethane and cooled to 0 under a nitrogen atmosphere ℃ . After cooling, 7.57 g (67.50 mmol) of aluminum chloride was slowly added thereto, followed by stirring for 30 minutes. 6.09 g (65.89 mmol) of propionyl chloride was diluted with 20 ml of dichloromethane, and the mixture was slowly added dropwise, followed by stirring at 0 ° C for 1 hour. The reaction was warmed to room temperature, stirred for 4 hours and then re-cooled to 0 ° C. After cooling, the reaction was terminated by slowly pouring into 200 ml of ice-distilled water. The organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain the product Photography (solvent: ethyl Oh glyphosate acid: n-hexane = 1: 8) to provide yellow 4-bis (1- (9-allyl -9 H - Fluorene-9-yl) -propan-1-one) butane (yield: 31%).

1 H-NMR (? Ppm: CDCl 3 ): 1.20-1.38 (6H, t), 1.42-1.58 (4H, m), 2.27-2.41 (4H, m), 3.11-3.27 M), 8.07-8.19 (4H, m), 3.70 (4H, m), 5.41-5.55 (4H, m), 6.27-6.39 (2H, m), 7.38-7.55 )

Step 3. Preparation of 1,4-bis (1- (9-allyl -9 H - fluoren-9-yl) -1,2-propane-dione-2-oxime) Preparation of butane

The 1,4-bis prepared in step 2, a (1 - (9-allyl -9 H - - fluoren-9-yl) propan-1-one) butane 10.0g (17.27mmol) in a nitrogen atmosphere tetrahydrofuran 40 ml of 4N hydrogen chloride (1,4-dioxane) and 5.06 g (43.19 mmol) of isopentyl nitrite were added thereto. And the mixture was stirred at room temperature for 4 hours. The reaction was poured slowly into 200 ml of distilled water and the reaction was terminated. The solid precipitate was filtered, dissolved in ethyl acetate, and washed sequentially with saturated sodium hydrogencarbonate and distilled water. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. After concentration under reduced pressure and the filtrate yellow solid 1,4-bis (1- (9-allyl -9 H - fluoren-9-yl) -1,2-propane-dione-2-oxime) butane 7.81g (71% ).

1 H-NMR (? Ppm: CDCl 3 ): 1.40-1.54 (4H, m), 2.24-2.43 (10H, m), 3.61-3.75 (4H, m), 5.42-5.58 (2H, m), 7.37-7.53 (6H, m), 7.74-7.87 (4H, m), 8.07-8.18 (4H, m), 8.37-8.42

Preparation butane 11. Step 4. Preparation of 1,4-bis (1-acetate (9-allyl -9 H - fluoren-9-yl) -1,2-propane-dione-2-oxime - - O)

The 1,4-bis prepared in Step 3 (1- (9-allyl -9 H - fluoren-9-yl) -1,2-propane-dione-2-oxime) butane 5.0g (7.85mmol), dichloro Methane, and 2.0 g (19.63 mmol) of acetic anhydride was added thereto. The reaction mixture was heated, stirred at 70 ° C for 5 hours, and cooled to room temperature. 20 ml of dichloromethane was added, and the mixture was washed successively with saturated sodium hydrogencarbonate and distilled water. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. After concentration under reduced pressure and the filtrate yellow solid 1,4-bis (1- (9-allyl -9 H - fluoren-9-yl) -1,2-propane-dione-2-oxime - O - acetate) butane 3.90 g (69%).

1 H-NMR (δ ppm: CDCl 3): 1.37-1.52 (4H, m), 2.20-2.39 (10H, m), 2.39-2.46 (6H, m), 3.58-3.71 (4H, m), 5.38- M), 8.07-8.20 (4H, m), 5.55 (4H, m), 6.18-6.30 (2H, m), 7.36-7.52

(Example 7) Preparation of photoresist composition

9.8 g of an alkali-soluble binder resin as a copolymer of benzyl methacrylate / methacrylic acid (molar ratio 70/30, molecular weight 20,000 g / mol, acid value 100 KOH mg / g), green pigment dispersion (CI Pigment Green 7, 20 wt% in PGMEA) , 10 g of dipentaerythritol hexaacrylate, 0.6 g of the fluorene derivative prepared in Example 1, 0.1 g of pentaerythritol tetrakis 3-mercaptobutyrate, 0.1 g of 2-methacryloxypropyltrimethoxysilane, And 49.4 g of propylene glycol monomethyl ether acetate (PGMEA) were sequentially mixed, and the mixture was stirred at room temperature for 3 hours to prepare a photoresist composition.

Evaluation of the photoresist composition prepared by the above method was performed on a glass substrate, and the performances such as sensitivity, residual film ratio, chemical resistance and developability of the photoresist composition were measured and the results are shown in Table 1 below.

1. Sensitivity

The above photoresist composition was spin-coated on a glass substrate and subjected to a heat treatment at 100 for 100 seconds, exposed using a step mask, and developed in a 0.04% KOH aqueous solution. The exposure amount at which the step mask pattern was maintained at 80% thickness with respect to the initial thickness was evaluated as sensitivity.

2. Residual film rate

After the photoresist composition was spin-coated on the substrate, it was subjected to a heat treatment at 100 for 100 seconds, followed by exposure at 365 nm, post-baking (post-baking) at 230 to 25 minutes, ) Were measured.

3. Chemical resistance

After the photoresist composition was spin-coated on the substrate, the resist film formed by the preheating treatment, the exposure treatment, the post-heat treatment, and the like was immersed in the NMP solution for 45 to 30 minutes, and then the appearance change of the resist film was observed.

At this time, it was indicated that the appearance change was not good (O), that slight change of state was detected (Δ), the appearance was peeled or the solvent color was changed, and the defect (X) was indicated.

4. Developability

Developability was evaluated by observing the development process when the exposed substrate was developed with a 0.04% KOH aqueous solution for 60 seconds. When the development was clean and the pattern after development was well formed, the development was good, but the development time was long A case in which the straightness of the pattern is not good, a case in which the pattern is not formed clearly and the straightness is also inferior due to poor developability is indicated by X. [

(Example 8) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 7 except that 0.5 g of the fluorene derivative prepared in Example 2 was used in place of the fluorene derivative prepared in Example 1, 7, the performances of the photoresist composition such as sensitivity, residual film ratio, chemical resistance and developability were measured and the results are shown in Table 1 below.

(Example 9) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 7 except that 0.5 g of the fluorene derivative prepared in Example 3 was used instead of the fluorene derivative prepared in Example 1, 7, the performances of the photoresist composition such as sensitivity, residual film ratio, chemical resistance and developability were measured and the results are shown in Table 1 below.

(Example 10) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 7 except that 0.5 g of the fluorene derivative prepared in Example 4 was used in place of the fluorene derivative prepared in Example 1, 7, the performances of the photoresist composition such as sensitivity, residual film ratio, chemical resistance and developability were measured and the results are shown in Table 1 below.

(Example 11) Preparation of photoresist composition

Except that 0.5 g of the fluorene derivative prepared in Example 5 was used in place of the fluorene derivative prepared in Example 1, a photoresist composition was prepared by the same composition and method as in Example 7, 7, the performances of the photoresist composition such as sensitivity, residual film ratio, chemical resistance and developability were measured and the results are shown in Table 1 below.

(Example 12) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 7 except that 0.5 g of the fluorene derivative prepared in Example 6 was used instead of the fluorene derivative prepared in Example 1, 7, the performances of the photoresist composition such as sensitivity, residual film ratio, chemical resistance and developability were measured and the results are shown in Table 1 below.

(Comparative Example 1) Preparation of photoresist composition

Except that 0.5 g of Irgacure OXE-01 (product of BASF, refer to the following structure) was used in place of the fluorene derivative prepared in Example 1, and then a photoresist composition was prepared by the same composition and method as in Example 7, The sensitivity, residual film ratio, chemical resistance and developability of the photoresist composition were measured by the method of Example 7, and the results are shown in Table 1 below.

(Irgacure OXE-01 structure)

Figure 112015081617890-pat00031

(Comparative Example 2) Preparation of photoresist composition

Except that 0.5 g of Irgacure OXE-02 (product of BASF, refer to the following structure) was used in place of the fluorene derivative prepared in Example 1, and then the photoresist composition was prepared in the same manner as in Example 7, The sensitivity, residual film ratio, chemical resistance and developability of the photoresist composition were measured by the method of Example 7, and the results are shown in Table 1 below.

(Irgacure OXE-02 structure)

Figure 112015081617890-pat00032

Figure 112015081617890-pat00033

As shown in Table 1, the photoresist composition containing the fluorene derivative according to the present invention is far superior in sensitivity to the photoresist composition of the comparative example, and has excellent properties such as residual film ratio, chemical resistance and developability Able to know. Therefore, the photoresist composition containing the fluorene derivative according to the present invention minimizes the outgassing generated from the photopolymerization initiator in the exposure and post-baking processes of the TFT-LCD manufacturing process, thereby reducing the contamination and minimizing the defects that may occur It is possible to provide a high-quality thin film.

Claims (11)

A fluorene derivative having an unsaturated group represented by the following formula (1);
[Chemical Formula 1]
Figure 112017060797821-pat00034

In the formula (1)
R 1, R 3 to R 6 and R 8 are each independently hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, or ( C3-C30) heteroaryl, R 2 is hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl Aryl, amino (-NH2), nitro (-NO2), cyano (-CN), C (= O)
Figure 112017060797821-pat00035
, R < 7 >
Figure 112017060797821-pat00036
And wherein n is an integer of 0 or 1, R 21 and R 23 to R 24 are each independently (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6 -C30) aryl, or (C3-C30) heteroaryl;
R 9 and R 10 are each independently (C1-C30) alkyl, (C2-C30) alkenyl or (C2-C30) and alkynyl, wherein R 9 and R 10 are connected to each other to form a ring, or (C1- C5) alkylene, (C2-C5) alkenylene, or (C6-C12) may form a dimer linked arylene, wherein R 9 or R 10 may be comprises a least one unsaturated, wherein R 9 And R < 10 > are linked together to form an alicyclic ring or an aromatic ring containing an unsaturated group;
Cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R 1 to R 8 and alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R 21 and R 23 to R 24 and R 9 and R 10 alkyl, alkenyl, alkynyl, and R 9 and R 10 are connected to each other formed ring are each independently (C1-C30) alkyl, (C2-C30) alkenyl, (C3-C30) cycloalkyl, (C3 (O) (OR a ) (OR b ), wherein R a and R b are each independently selected from the group consisting of (C 1 -C 30) heterocycloalkyl, and P (C3-C30) heterocycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl, wherein said heterocycloalkyl and Heteroaryl comprises at least one heteroatom selected from B, N, O, S, P (= O), Si and P. The method according to claim 1,
Wherein R 9 and R 10 are each independently (C1-C10) alkyl, (C2-C10) alkenyl or (C2-C10) alkynyl, and wherein R 9 and R 10 are optionally substituted with a methylene (C1 C5) alkylene or (C2-C5) alkenylene to form a ring, or a dimer connected with (C1-C5) alkylene, (C2-C5) alkenylene or And R < 9 > or R < 10 > must contain at least one unsaturated group. The method according to claim 1,
A fluorene derivative represented by the following formula (2);
(2)
Figure 112017060797821-pat00037

In the formula (2)
R 1, R 3 to R 6 and R 8 are each independently hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, or ( C3-C30) heteroaryl;
R 9 and R 10 are each independently (C1-C30) alkyl, (C2-C30) alkenyl or (C2-C30) and alkynyl, wherein R 9 and R 10 are connected to each other to form a ring, or (C1- C5) alkylene, (C2-C5) alkenylene, or (C6-C12) may form a dimer linked arylene, wherein R 9 or R 10 may be comprises a least one unsaturated, wherein R 9 And R < 10 > are linked together to form an alicyclic ring or an aromatic ring containing an unsaturated group;
R 21 , R 23 and R 24 are each independently selected from the group consisting of (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C6-C30) aryl, or (C3-C30) heteroaryl;
n and m are each independently an integer of 0 or 1;
Alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R 1 , R 3 to R 6 and R 8 and alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R 21 and R 23 to R 24 , wherein R 9 and the alkyl of R 10, alkenyl, alkynyl, and R 9 and R 10 are connected to each other formed ring are each independently (C1-C30) alkyl, (C2-C30) alkenyl, (C3-C30) (O) (OR a ) (OR b ), wherein R a and R b are each independently selected from the group consisting of (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl, Heterocycloalkyl and heteroaryl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P. The method of claim 3,
Wherein R 9 and R 10 are each independently (C1-C10) alkyl, (C2-C10) alkenyl or (C2-C10) alkynyl, and wherein R 9 and R 10 are optionally substituted with a methylene (C1 C5) alkylene or (C2-C5) alkenylene to form a ring or a dimer connected with (C1-C5) alkylene, (C2-C5) alkenylene or And R < 9 > or R < 10 > must contain at least one unsaturated group. The method according to claim 1,
A fluorene derivative represented by the following formula (3);
(3)
Figure 112017060797821-pat00040

In Formula 3,
R 1, R 3 to R 6 and R 8 are each independently hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, or ( C3-C30) heteroaryl;
R 9 is (C1-C30) alkyl, (C2-C30) alkenyl or (C2-C30) alkynyl;
M comprises (C1-C5) alkylene, (C2-C5) alkenylene, or (C6-C12) may form a dimer linked arylene, wherein R 9 or M must be an at least one unsaturation, and ;
R 21, R 23 and R 24 are each independently (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, or (C3-C30) heteroaryl Aryl;
n and m are each independently an integer of 0 or 1;
Alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R 1 , R 3 to R 6 and R 8 and alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R 21 and R 23 to R 24 , alkenyl alkyl, eggs of the R 9, alkynyl are each independently (C1-C30) alkyl, (C2-C30) alkenyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, and P (= O) (OR a) (OR b) a may be further substituted with one or more substituents selected from the group consisting of, wherein R a, and R b are each independently (C1-C30) alkyl, (C2-C30) alkenyl (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl, said heterocycloalkyl and heteroaryl being optionally substituted with B, N, O, S, P (= O), Si and P. The method according to claim 1,
A fluorene derivative selected from the following structures;
Figure 112015081617890-pat00043

Figure 112015081617890-pat00044

Figure 112015081617890-pat00045

Figure 112015081617890-pat00046
 A photopolymerization initiator comprising the fluorene derivative according to claim 1. A photoresist composition comprising the fluorene derivative according to any one of claims 1 to 6 and a colorant. The photoresist composition according to claim 8, further comprising a photosensitizer containing a thiol group. 9. A color filter comprising the photoresist composition according to claim 8. A black matrix comprising the photoresist composition according to claim 8.
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WO2014050738A1 (en) 2012-09-28 2014-04-03 ダイトーケミックス株式会社 Fluorene-type compound, photopolymerization initiator comprising said fluorene-type compound, and photosensitive composition containing said photopolymerization initiator
KR101435652B1 (en) 2014-01-17 2014-08-28 주식회사 삼양사 NOVEL FLUORENYL β-OXIME ESTER COMPOUNDS, PHOTOPOLYMERIZATION INITIATOR AND PHOTORESIST COMPOSITION CONTAINING THE SAME

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US4590145A (en) 1985-06-28 1986-05-20 Daicel Chemical Industries, Ltd. Photopolymerization initiator comprised of thioxanthones and oxime esters
EP1395615B1 (en) 2001-06-11 2009-10-21 Basf Se Oxime ester photoinitiators having a combined structure
JP4830310B2 (en) 2004-02-23 2011-12-07 三菱化学株式会社 Oxime ester-based compound, photopolymerizable composition, and color filter using the same
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KR101435652B1 (en) 2014-01-17 2014-08-28 주식회사 삼양사 NOVEL FLUORENYL β-OXIME ESTER COMPOUNDS, PHOTOPOLYMERIZATION INITIATOR AND PHOTORESIST COMPOSITION CONTAINING THE SAME

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