KR101831358B1 - Photoactive compound, photopolymerization initiator and photoresist composition containing the same - Google Patents

Photoactive compound, photopolymerization initiator and photoresist composition containing the same Download PDF

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KR101831358B1
KR101831358B1 KR1020160068508A KR20160068508A KR101831358B1 KR 101831358 B1 KR101831358 B1 KR 101831358B1 KR 1020160068508 A KR1020160068508 A KR 1020160068508A KR 20160068508 A KR20160068508 A KR 20160068508A KR 101831358 B1 KR101831358 B1 KR 101831358B1
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heteroaryl
aryl
alkynyl
cycloalkyl
alkenyl
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KR20170136698A (en
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김성현
김상하
허윤희
김다은
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(주)켐이
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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Abstract

The present invention relates to a novel photoactive compound, a photopolymerization initiator containing the same, and a photoresist composition. The photoactive compound according to the present invention is capable of effectively absorbing ultraviolet light as compared with the conventional photopolymerization initiator and has high sensitivity, And a photopolymerization initiator composition and photoresist composition which can realize an excellent residual film ratio, developability and strength.

Description

TECHNICAL FIELD The present invention relates to a photoactive compound, a photopolymerization initiator containing the same, and a photoresist composition containing the photopolymerization initiator and photoresist composition,

The present invention relates to a photoactive compound, a photopolymerization initiator and a photoresist composition containing the same, and more particularly, to a novel photoactive compound comprising oxime ester group and phosphonate group simultaneously, a photopolymerization initiator and photoresist composition .

Photopolymerization represents a process of polymerizing (curing) a monomer, oligomer or polymer matrix under light induction, and this technique is widely used in photocurable ink, packaging materials for liquid crystal panels, photosensitive printing plates, color filters, photoresists and the like. The point of the photopolymerization technique is to cause the polymerization of the unsaturated groups of the polymerizable monomers using a photoinitiator activated under irradiation of a light source having a specific wavelength, resulting in polymerization of the material. At this time, the photoinitiator is a very important factor affecting the photopolymerization initiator composition, the photoresist composition (photosensitive composition) and the like.

There are a number of studies and reports of conventional photoinitiators. However, these photoinitiators generally have low photo-sensing activity and have serious limitations in terms of the types of light sources that can be applied. Also, most of them are only suitable for ultraviolet excitation. For example, the acetophenone derivatives disclosed in Patent Document 1 are good in color characteristics and solubility and relatively inexpensive. However, in order to obtain sufficient sensitivity, acetophenone derivatives are required to use at least 3%, even at least 10%, of the solid content, It may be a cause of liquid crystal contamination. In a composition having a high pigment concentration, particularly a black photosensitive composition, the sensitivity is insignificant, so that there is a problem that desorption of a pattern is seriously occurred when used alone. The oxime ester derivative disclosed in Patent Document 2 has a problem that it has little color and high transmittance and is excellent in stability and compatibility in a composition but is not efficient in absorbing a UV light source and thus takes a long process time. There is still a difficulty in forming a fine pattern because the curing degree of the thick film having a thickness of 2.5 탆 or more is not sufficiently satisfied and the formed pattern can not satisfy the CD (critical dimension) or the mechanical strength required in the product. In the triazine derivatives disclosed in Patent Document 3, halomethyltriazine derivatives which are decomposed by light irradiation to generate halogen radicals are known to have good sensitivity to a UV light source as compared with the photopolymerization initiators described above, It tends to precipitate on the posterior surface or to crystallize rapidly in the film. In addition, the carbazolyl oxime ester type photoinitiator disclosed in Patent Document 4 has a disadvantage that it meets only the requirements for the use of mercury lamps (including high-pressure, intermediate-pressure and low-pressure mercury lamps) as an exposure light source.

Recently, we have developed a photoinitiator that can match with low energy and long wavelength-output exposure light sources such as LED (Light Emitting Diode) and LDI (LCD Driver Interface) Research and development have important practical and economic implications.

Taking this into consideration, the Applicant has solved the problems as described above, and has found that a novel photoactive compound capable of satisfying the needs of industry and reducing cost and having characteristics such as higher sensitivity, excellent thermal stability and storage stability The present invention provides a photopolymerization initiator and a photoresist composition.

1) United States Patent No. 4590145 2) United States Patent No. 4255513 3) Japanese Laid-Open Patent Application No. 2013-531086 4) China Patent No. 101508744

An object of the present invention is to provide a novel photoactive compound that absorbs a broader range of ultraviolet light than conventional photopolymerization initiators and has remarkably improved sensitivity, heat resistance and chemical resistance.

Another object of the present invention is to provide a photopolymerization initiator composition and a photoresist composition which can realize excellent physical properties such as residual film ratio, developability and strength even with a smaller amount of use.

The present invention provides a novel photoactive compound represented by the following formula (1).

[Chemical Formula 1]

Figure 112016053186677-pat00001

In the formula (1)

Ar 1 to Ar 3 are each independently hydrogen, -SR 11, -NR 12 R 13 , (C6-C30) aryl and (C3-C30) heteroaryl or more selected from selected from Ar 1 to Ar 3 are connected to each other It is can form a ring, wherein R 11 to R 13 are each independently hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl Or (C3-C30) heteroaryl;

Ar 4 is a single bond or (C1-C30) alkylene;

R 1 is hydrogen, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;

R 2 is (C 2 -C 30) alkenyloxy, (C 2 -C 30) alkynyloxy or -OL 1 -OC (═O) -R 14 , R 3 is (C 6 -C 30) aryl, heteroaryl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C2-C30) alkenyloxy, (C2-C30) alkynyloxy or -OL 1 -OC (= O) -R 14 , and , R 14 is (C 2 -C 30) alkenyl, (C 2 -C 30) alkynyl, R 2 and R 3 may be connected to each other to form a ring, L 1 is (C 1 -C 30) ;

n is an integer of 0 or 1;

Wherein Ar 1 to Ar 3 of the aryl, heteroaryl and the ring, the R 1 alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl, alkenyl of R 2 and R 3, alkynyl or rings are independently (C1, respectively (C3-C30) alkenyl, (C2-C30) alkynyl, (C3-C30) cycloalkyl, (C3- C30) heterocycloalkyl, (C6- heteroaryl, cyano, nitro, -CR 24, -OR 21, -SR 22, -NR 21 R 22, -C (= O) R 23, -C (= O) OR 23, -C (= O) NR 21 R 22 and -L 2 -P (= O) (OR 21 ) (OR 22 ), and R 21 To R 23 are each independently selected from hydrogen, heavy hydrogen (deuterium), (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C3-C30) cycloalkyl (C1-C30) alkyl , (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, (C1-C30) alkyl (C6-C30) aryl or (C3-C30) heteroaryl, wherein R 24 is a halogen, wherein L 2 is an alkylene single bond or a (C1-C30), wherein said heterocycloalkyl and heteroaryl is B, N, O, S, P (= O), one or more heteroatoms selected from Si and P Atoms.]

The photoactive compound according to one embodiment of the present invention may be represented by the following formula (2).

(2)

Figure 112016053186677-pat00002

In the formula (2)

Ar 1 and Ar 2 are each independently selected from hydrogen, -SR 11 , (C 6 -C 20) aryl and (C 3 -C 20) heteroaryl,

Figure 112016053186677-pat00003
,
Figure 112016053186677-pat00004
or
Figure 112016053186677-pat00005
A can form a ring, wherein R 11 is (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl or (C3-C20) heteroaryl, and wherein R 31 to R 36 are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl, (C3-C20) heteroaryl, cyano, nitro or -L 2 -P (= O) ( oR 21) (oR 22) a, wherein L 2 is a single bond or alkylene (C1-C30), wherein R 21 And R 22 are each independently (C 2 -C 30) alkenyl or (C 2 -C 30) alkynyl;

Ar 4 is a single bond or (C 1 -C 20) alkylene;

n is an integer of 0 or 1;

R 1 is hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) heteroaryl;

R 2 is (C 2 -C 20) alkenyloxy or (C 2 -C 20) alkynyloxy, R 3 is (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, -C20) alkynyl, (C2-C20) alkenyloxy, (C2-C20) alkynyloxy or -OL 1 -OC (= O) and -R 14, wherein R 14 is (C2-C20) alkenyl, (C2-C20) alkynyl, R 2 and R 3 may be connected to each other to form a ring, L 1 is (C 1 -C 20) alkylene, the ring is (C 1 -C 20) C20) alkenyl, (C2-C20) alkynyl, (C3-C20) cycloalkyl and (C3-C20) heterocycloalkyl.

R 2 of the photoactive compound according to an embodiment of the present invention is (C 2 -C 7 ) alkenyloxy, (C 2 -C 7 ) alkynyloxy or -OL 1 -OC (═O) -R 14 , and R 3 (C2-C7) alkynyl, (C2-C7) alkenyloxy, (C2-C7) alkynyloxy or -OL 1 -OC (= O) and -R 14, L 1 is (C1-C7) alkylene, wherein R 14 is (C2-C7) alkenyl, (C2-C7) alkynyl is, the R 2 And R < 3 >

Figure 112016053186677-pat00006
or
Figure 112016053186677-pat00007
A can form a ring, wherein R 41 and R 42 are each independently hydrogen, (C2-C7) alkenyl, (C2-C7) alkynyl, (C3-C20) cycloalkyl or (C3-C20) heteroaryl And is cycloalkyl.

Ar 4 of the photoactive compound according to an embodiment of the present invention may be (C 1 -C 7) alkylene.

The photoactive compound according to one embodiment of the present invention may be selected from the following structures, but is not limited thereto.

Figure 112016053186677-pat00008

Figure 112016053186677-pat00009

Figure 112016053186677-pat00010

The present invention provides a photopolymerization initiator composition and a photoresist composition comprising the photoactive compound represented by Formula 1 above. In particular, it has a very high sensitivity to an exposure light source such as an LED, LDI, etc. having low energy and long wavelength output, and is expected to be used commercially.

In addition, the present invention can efficiently absorb ultraviolet rays using the above-described photoactive compound and provide a color filter or a black matrix with excellent sensitivity, excellent residual film ratio, mechanical strength, heat resistance, chemical resistance, Particularly, in the case of a black matrix using a high coloring agent to adjust the optical density, even a small amount of the black matrix exhibits high sensitivity compared to the same exposure amount, thereby realizing more improved physical characteristics.

The photoactive compound according to the present invention has a high sensitivity to a wide range of ultraviolet light sources, and can exhibit very high sensitivity to an exposure light source such as LED, LDI, etc., and has high solubility and coloring matters, multi functional monomer Binder resin and the like, and it has an advantage that the defective rate can be minimized by effectively suppressing the outgassing occurring in the exposure and post-baking process due to the high thermal stability.

The photoresist composition containing the photoactive compound having a high sensitivity according to the present invention can remarkably improve the polymerization and curing reaction rate of the polymerizable compound having unsaturated bonds by irradiation with light, And the rate of curing reaction can be suitably controlled to achieve the desired physical properties.

Further, since the photoresist composition according to the present invention can realize excellent reactivity even at a low exposure dose, even in the case of a black matrix in which a high colorant is to be used, the photoresist composition has remarkably improved residual film ratio, mechanical strength, heat resistance, And further react with a photosensitizer containing a reactive group such as a thiol group or a silyl group to produce an improved retention rate, mechanical strength, heat resistance, chemical resistance and resistance to rust.

Accordingly, the photoactive compound according to the present invention is advantageous not only in curing of a column spacer, an overcoat, a passivation material, etc. of a liquid crystal display device but also in a high temperature process characteristic.

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

Since the photoactive compound according to the present invention has a phosphonate group containing an unsaturated group, it has excellent sensitivity and effectively suppresses the outgassing occurring in the exposure and post-bake process due to high thermal stability, thereby minimizing the generation of contaminated waste It is possible to provide a photosensitive material having a high purity.

Further, the photoactive compound according to the present invention is excellent in compatibility with an additive added to a photoinitiator composition, a photoresist (photosensitive material) composition and the like, and solubility in a solvent.

The photoactive compound according to the present invention can be represented by the following formula (1).

[Chemical Formula 1]

Figure 112016053186677-pat00011

In the formula (1)

Ar 1 to Ar 3 are each independently hydrogen, -SR 11, -NR 12 R 13 , (C6-C30) aryl and (C3-C30) heteroaryl or more selected from selected from Ar 1 to Ar 3 are connected to each other It is can form a ring, wherein R 11 to R 13 are each independently hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl Or (C3-C30) heteroaryl;

Ar 4 is a single bond or (C1-C30) alkylene;

R 1 is hydrogen, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;

R 2 is (C 2 -C 30) alkenyloxy, (C 2 -C 30) alkynyloxy or -OL 1 -OC (═O) -R 14 , R 3 is (C 6 -C 30) aryl, heteroaryl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C2-C30) alkenyloxy, (C2-C30) alkynyloxy or -OL 1 -OC (= O) -R 14 , and , R 14 is (C 2 -C 30) alkenyl, (C 2 -C 30) alkynyl, R 2 and R 3 may be connected to each other to form a ring, L 1 is (C 1 -C 30) ;

n is an integer of 0 or 1;

Wherein Ar 1 to Ar 3 of the aryl, heteroaryl and the ring, the R 1 alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl, alkenyl of R 2 and R 3, alkynyl or rings are independently (C1, respectively (C3-C30) alkenyl, (C2-C30) alkynyl, (C3-C30) cycloalkyl, (C3- C30) heterocycloalkyl, (C6- heteroaryl, cyano, nitro, -CR 24, -OR 21, -SR 22, -NR 21 R 22, -C (= O) R 23, -C (= O) OR 23, -C (= O) NR 21 R 22 and -L 2 -P (= O) (OR 21 ) (OR 22 ), and R 21 To R 23 are each independently selected from hydrogen, heavy hydrogen (deuterium), (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C3-C30) cycloalkyl (C1-C30) alkyl , (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, (C1-C30) alkyl (C6-C30) aryl or (C3-C30) heteroaryl, wherein R 24 is a halogen, wherein L 2 is an alkylene single bond or a (C1-C30), wherein said heterocycloalkyl and heteroaryl is B, N, O, S, P (= O), one or more heteroatoms selected from Si and P Atoms.]

The photoactive compound according to the present invention is excellent in efficiency of absorbing a wide range of ultraviolet rays to generate radicals and functions as an effective initiator for polymerization and curing reaction of polymerizable compounds having various unsaturated groups, Mechanical strength, heat resistance, chemical resistance, and developability of the photosensitive material produced therefrom can be remarkably improved.

At this time, the photosensitive material is a photosensitive material for forming a black matrix such as a pigment dispersed type photosensitive material for TFT LCD color filter, a TFT LCD and an organic light emitting diode, a photosensitive material for forming an overcoat layer, a photosensitive material for a column spacer, A photosensitive material for a printing wiring board, and the like, but is not limited thereto.

The term "single bond" of the present invention means a direct bond, and all substituents including the term "alkyl "," alkoxy ", and other "alkyl" moieties of the present invention include hydrocarbon radicals including both linear and branched forms It can be meaningful. In this case, the alkyl is preferably (C1-C20) may be an alkyl, more preferably methyl, ethyl, n - propyl, i - propyl, n - butyl, i - butyl, s - butyl, t - butyl, but is not limited to, a lower hydrocarbon radical selected from n -pentyl, i -pentyl, s -pentyl, n -hexyl, i -hexyl, s -hexyl,

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- Di-2-yl, and the like, but is not limited thereto. The term "alkynyl" means an unsaturated hydrocarbon radical in the form of a straight or branched chain containing at least one triple bond, and specific examples thereof include ethynyl, prop-1-yn-1-yl, 1-yl, -but-1-yn-1-yl, but-1-yn-3-yl or but-3-yn-1-yl and the like.

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 aromatic radical derived from aromatic hydrocarbons by 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.

The term "alkylene" or "alkenylene" in the present invention means a residual divalent residue after removal of one hydrogen atom from (C1-C20) May have a carbon number of C2 to C7, but the present invention is not limited thereto.

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

The photoactive compound according to an embodiment of the present invention is excellent in low-temperature storage stability and is a photoactive compound represented by the following formula (2) in view of not producing fouled materials such as fume during the production of photosensitive material have.

(2)

Figure 112016053186677-pat00012

In the formula (2)

Ar 1 and Ar 2 are each independently selected from hydrogen, -SR 11 , (C 6 -C 20) aryl and (C 3 -C 20) heteroaryl,

Figure 112016053186677-pat00013
,
Figure 112016053186677-pat00014
or
Figure 112016053186677-pat00015
A can form a ring, wherein R 11 is (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl or (C3-C20) heteroaryl, and wherein R 31 to R 36 are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl, (C3-C20) heteroaryl, cyano, nitro or -L 2 -P (= O) ( oR 21) (oR 22) a, wherein L 2 is a single bond or alkylene (C1-C30), wherein R 21 And R 22 are each independently (C 2 -C 30) alkenyl or (C 2 -C 30) alkynyl;

Ar 4 is a single bond or (C 1 -C 20) alkylene;

n is an integer of 0 or 1;

R 1 is hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) heteroaryl;

R 2 is (C 2 -C 20) alkenyloxy or (C 2 -C 20) alkynyloxy, R 3 is (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, -C20) alkynyl, (C2-C20) alkenyloxy, (C2-C20) alkynyloxy or -OL 1 -OC (= O) and -R 14, wherein R 14 is (C2-C20) alkenyl, (C2-C20) alkynyl, R 2 and R 3 may be connected to each other to form a ring, L 1 is (C 1 -C 20) alkylene, the ring is (C 1 -C 20) C20) alkenyl, (C2-C20) alkynyl, (C3-C20) cycloalkyl and (C3-C20) heterocycloalkyl.

In addition, the photoactive compound according to an embodiment of the present invention has a phosphonate group including an oxime ester group and a specific unsaturated group, thereby realizing high sensitivity even under a low energy, long wavelength-output exposure light source, Or the like, and can form a fine pattern having high adhesion to the substrate and high strength with remarkably improved sensitivity by reacting with a photosensitizer having a reactive substituent such as a group.

The photoactive compound according to one embodiment of the present invention may be represented by the following formulas (3) to (6), but is not limited thereto.

(3)

Figure 112016053186677-pat00016

[Chemical Formula 4]

Figure 112016053186677-pat00017

[Chemical Formula 5]

Figure 112016053186677-pat00018

[Chemical Formula 6]

Figure 112016053186677-pat00019

[In formulas (3) to (6)

Ar 4 is a single bond or (C 1 -C 7) alkylene;

R 1 is hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) heteroaryl;

R 2 is (C 2 -C 20) alkenyloxy or (C 2 -C 20) alkynyloxy, R 3 is (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, -C20) alkynyl, (C2-C20) alkenyloxy, (C2-C20) alkynyloxy or -OL 1 -OC (= O) and -R 14, wherein R 14 is (C2-C20) alkenyl, (C2-C20) alkynyl, R 2 and R 3 may be connected to each other to form a ring, L 1 is (C 1 -C 20) alkylene, the ring is (C 1 -C 20) C20) alkenyl, (C2-C20) alkynyl, (C3-C20) cycloalkyl and (C3-C20) heterocycloalkyl;

n is an integer of 0 or 1;

R 31 to R 36 are each independently selected from the group consisting of hydrogen, (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl, cyano, nitro or -L 2 -P (= O) ( oR 21) (oR 22) a, wherein L 2 is a single bond or alkylene (C1-C30), wherein R 21 And R 2 are each independently (C 2 -C 30) alkenyl or (C 2 -C 30) alkynyl;

R 51 is (C6-C20) aryl or (C3-C20) heteroaryl.

R 2 in the optically active compound in accordance with one embodiment of the present invention, (C2-C7) alkenyloxy, (C2-C7) alkynyloxy or -OL 1 -OC (= O) -R 14 , and a, R 3 is (C2-C7) alkynyl, (C2-C7) alkynyl, (C2-C7) and OL 1 -OC (= O) -R 14, L 1 is (C1-C7) alkylene, wherein R 14 is (C2-C7) alkenyl, (C2-C7), and alkynyl, wherein R 2 and R 3 is connected

Figure 112016053186677-pat00020
or
Figure 112016053186677-pat00021
A can form a ring, wherein R 41 and R 42 are each independently hydrogen, (C2-C7) alkenyl, (C2-C7) alkynyl, (C3-C20) cycloalkyl or (C3-C20) heteroaryl And R 41 and R 42 may be connected to each other to form a ring. Wherein the ring may be one selected from (C3-C30) cycloalkyl and (C3-C30) heterocycloalkyl, but is not limited thereto.

The substituent which can be substituted at the position of R 3 is not limited, but it is preferably used in combination with a photosensitizer containing a thiol group, a silyl group or the like in view of formation of a high-purity light-sensitive material and a fine pattern with excellent sensitivity Phenyl, naphthyl, biphenyl or the following structures.

Figure 112016053186677-pat00022

In addition, the photoactive compound according to an embodiment of the present invention can realize sufficient sensitivity as a photopolymerization initiator even in a small amount, minimizing contamination sources of the liquid crystal to improve the residual film ratio of the pattern, from the side having the advantage of increasing, Ar 4 is (C1-C7) is not one that preferably the alkylene is not limited thereto.

The photoactive compound according to one embodiment of the present invention may be selected from the following structures in view of having a very high sensitivity even under a light source having a low energy and a long wavelength output even in a small amount of use, But is not limited thereto.

Figure 112016053186677-pat00023

Figure 112016053186677-pat00024

Figure 112016053186677-pat00025

The photoactive compound according to the present invention not only remarkably improves the UV light absorption rate but also can control the pattern properties of the composition of the photoresist according to the substituent change and control the physical properties of the thin film such as heat resistance and chemical resistance. That is, the composition of the photoresist according to the present invention can be applied to a black matrix, a color filter, a column spacer, an organic insulating film, a photoresist composition for an overcoat, and the like, and can be effectively applied to a black matrix requiring a high colorant.

The present invention provides a photopolymerization initiator composition comprising the photoactive compound.

The present invention also provides a photoresist composition comprising the photoactive compound.

The photoresist composition according to the present invention comprises a binder resin, a colorant, and a photoactive compound according to the present invention. The photoactive compound may be contained in an amount of 0.01 to 15% by weight based on 100% by weight of the total photoresist composition. , Preferably 0.01 to 10% by weight, and more preferably 0.01 to 5% by weight, may minimize the contamination by the by-product decomposed after photo-initiation.

The binder resin is not limited as long as it is known in the art, but it has an average molecular weight of 2,000 to 300 and a dispersity of 1.0 to 10.0 in terms of high degree of miscibility with the photoactive compound according to the present invention Acrylic polymers, novolac resins, 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 organic pigments and inorganic pigments can be compounds classified as pigments in the color index (published by The Society of Dyers and Colourists), and more specific examples include CI Pigment Yellow 13, 20, 24, 31, 53 , 83, 86, 93, 94, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; CI Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76; CI Pigment Green 7, 10, 15, 25, 36, 47 and 58; CI Pigment Brown 28; CI Pigment Black 1 and 7, Lactam Black, and Pigments of Color Index (CI) number. 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, it is preferable that the photosensitizer has a reactive substituent such as a thiol group and a silyl group, and the photosensitizer containing the photosensitizer may react sensitively with the photoactive compound according to the present invention, And the residual film ratio and developability of a color filter, a black matrix, and the like manufactured using the same can be significantly improved.

The photosensitizer having high reactivity with the photoactive compound according to the present invention is not limited as long as it contains a thiol group, a silyl group, and the like. Nonlimiting examples thereof include pentaerythritol tetrakis thioglycolate, pentaerythritol tetrakis thioglycolate, A photosensitizer containing a thiol group such as pentaerythritol tetrakis thiopropionate and pentaerythritol tetrakis (3-mercapto butylate); ≪ / RTI > In addition, the photoactive compound according to the present invention may be produced by reacting a reactive substituent such as a thiol group or a silyl group with a hydrosilylation reaction, a thiol-olefin addition reaction, a thiol-acetylene addition reaction And the like.

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 photoactive compound according to the present invention.

In addition, the photoresist composition according to the present invention may further contain a solvent other than the photosensitizer containing the colorant, the photoactive compound, the binder resin and the reactive group (thiol group, silyl group, etc.), the adhesion aid, ≪ / RTI > and the like.

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 is 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.

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).

(Example 1) Preparation of Compound 1

Step 1. Preparation of compound 1-a

Figure 112016053186677-pat00026

20.0 g (107.37 mmol) of diphenyl sulfane and 16.36 g (128.84 mmol) of 3-chloropropanyl chloride were dissolved in 200 ml of dichloromethane, and 14.46 g (128.84 mmol) of aluminum chloride was slowly added thereto at 0 ° C. The mixture was stirred at 0 ° C for 2 hours and further at room temperature for 2 hours. The reaction mixture was slowly poured into 400 ml of ice distilled water. After completion of the reaction, 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: 10) to obtain 22.0 g (yield: 74%) of the compound 1-a

1 H-NMR (δ ppm: CDCl 3): 2.32 (2H, t), 3.41 (2H, t), 7.15-7.24 (3H, m), 7.40-7.45 (2H, d), 7.51-7.55 (2H, d), 7.72-7.78 (2H, d)

Step 2. Preparation of compound 1-b

Figure 112016053186677-pat00027

 11.96 g (205.94 mmol) of allyl alcohol and 20.84 g (205.94 mmol) of triethylamine were dissolved in 150 ml of dichloromethane and maintained at 0 ° C. Then, 8.93 g (65.03 mmol) of phosphorus trichloride was diluted in 50 ml of dichloromethane And the mixture was stirred at room temperature for 1 hour. The reaction product is separated into a precipitate and a filtrate using a filter paper. The filtrate was diluted with ethyl acetate and washed with distilled water. 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 dissolved in 20 ml of dimethylacetamide. 15.0 g (54.19 mmol) of 1-a prepared in the above step 1 was added. The reaction was heated to 110 ° 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: 4) to obtain 16.55 g (yield: 54%) of compound 1-b.

1 H-NMR (? Ppm: CDCl 3 ): 2.28-2.35 (4H, m), 4.16-4.25 (4H, m), 5.10-5.15 (2H, d), 7.50-7.57 (2H, d), 7.70-7.75 (2H, d)

Step 3. Preparation of compound 1-c

Figure 112016053186677-pat00028

10.0 g (24.84 mmol) of 1-b prepared in the above step 2 was dissolved in 100 ml of dimethylacetamide under nitrogen atmosphere, and 2.59 g (37.27 mmol) of hydroxyamine hydrochloride was added dropwise. The reaction product was heated, stirred at 70 ° C for 2 hours, and cooled to room temperature. The reaction was poured slowly into 200 ml of distilled water, and after completion of the reaction, 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 to obtain 7.46 g (72%) of the compound 1-c.

1 H-NMR (δ ppm: CDCl 3): 2.22-2.32 (4H, m), 4.17-4.27 (4H, m), 5.11-5.15 (2H, d), 5.25-5.33 (2H, d), 5.85- (2H, d), 7.74-7.79 (2H, d), 11.02-11.15 (1H, s), 7.98-7.79 )

Step 4. Preparation of Compound 1

Figure 112016053186677-pat00029

1.82 g (17.96 mmol) of 1-c, triethylamine prepared in the above step 3 was dissolved in 50 ml of dichloromethane, and the mixture was cooled to 0 占 폚. 2.77 g (17.96 mmol) of 2-methylbenzoyl chloride was diluted in 10 ml of dichloromethane and slowly added dropwise. The mixture was stirred at 0 ° C for 1 hour and then at room temperature for 2 hours. The reaction mixture was slowly poured into 100 ml of ice-distilled water. After completion of the reaction, 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: 4) to obtain 4.36 g of Compound 1 (yield: 68%).

1 H-NMR (δ ppm: CDCl 3): 2.20-2.35 (7H, m), 4.18-4.26 (4H, m), 5.15-5.21 (2H, d), 5.28-5.37 (2H, d), 5.91- (2H, m), 7.15-7.28 (4H, m), 7.35-7.46 (3H, m), 7.55-7.62 (3H, m), 7.78-7.85 )

(Example 2) Preparation of Compound 3

Step 1. Preparation of compound 3-a

Figure 112016053186677-pat00030

20.0 g (107.37 mmol) of diphenyl sulfane and 18.17 g (128.84 mmol) of 3-chlorobutane chloride were dissolved in 200 ml of dichloromethane, and 14.46 g (128.84 mmol) of aluminum chloride was slowly added thereto at 0 ° C. The mixture was stirred at 0 ° C for 2 hours and further at room temperature for 2 hours. The reaction mixture was slowly poured into 200 ml of ice-distilled water. After completion of the reaction, 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: 10) to obtain 23.10 g (yield: 74%) of the compound 3-a.

1 H-NMR (δ ppm: CDCl 3): 1.52 (2H, m), 2.24 (2H, t), 3.50 (2H, t), 7.13-7.24 (3H, m), 7.40-7.47 (2H, d) , 7.50-7.56 (2H, d), 7.72-7.79 (2H, d)

Step 2. Preparation of compound 3-b

Figure 112016053186677-pat00031

20.0 g (68.77 mmol) of 3-a and 12.76 g (82.53 mmol) of 2-methylbenzoyl chloride prepared in the above step 1 were dissolved in 200 ml of dichloromethane, and 9.26 g (82.53 mmol) of aluminum chloride was slowly added at 0 ° C . The mixture was stirred at 0 ° C for 2 hours and further at room temperature for 6 hours. The reaction mixture was slowly poured into 200 ml of ice-distilled water. After completion of the reaction, 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 21.93 g (yield: 78%) of the compound 3-a

1 H-NMR (δ ppm: CDCl 3): 1.57 (2H, m), 2.27 (2H, t), 2.42 (3H, s), 3.58 (2H, t), 7.32-7.39 (1H, t), 7.40 (1H, d), 7.50-7.65 (3H, m), 7.68-7.84 (4H, m), 8.07-8.15

Step 3. Preparation of compound 3-d

Figure 112016053186677-pat00032

10.0 g (18.70 mmol) of 3-c prepared in the same manner as in Example 1, except that 3-b was used instead of 1-a, was dissolved in 80 ml of tetrahydrofuran under a nitrogen atmosphere 20 ml of 4N hydrogen chloride (1,4-dioxane) and 2.63 g (22.45 mmol) of isopentyl nitrite were added thereto, followed by stirring at room temperature for 4 hours. The reaction was poured slowly into 100 ml of distilled water and the reaction was terminated. Extracted with 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. The filtrate was concentrated under reduced pressure to obtain 7.27 g (yield: 69%) of the compound 3-d.

1 H-NMR (δ ppm: CDCl 3): 2.24-2.35 (7H, m), 4.16-4.25 (4H, m), 5.15-5.21 (2H, d), 5.27-5.35 (2H, d), 5.90- (1H, m), 7.99 (2H, m), 7.33-7.41 (1H, t), 7.41-7.48 ), 11.11 (1H, s)

Step 4. Preparation of compound 3

Figure 112016053186677-pat00033

5.0 g (8.87 mmol) of 3-d prepared in the above step 3 was dissolved in 40 ml of ethyl acetic acid, and 1.356 g (13.30 mmol) of acetic anhydride was added. The reaction mixture was heated to 80 DEG C for 2 hours, and then cooled to room temperature. The reaction was slowly added dropwise to 100 ml of hexane. The resulting solid precipitate was filtered and then dried to obtain 4.03 g (75%) of Compound 3

1 H-NMR (? Ppm: CDCl 3 ): 2.20-2.44 (10H, m), 4.15-4.23 (4H, m), 5.12-5.20 (1H, m), 7.95-7.88 (4H, m), 8.05-8.22 (3H, m), 7.31-7.40 )

(Example 3) Preparation of Compound 3

Step 1. Preparation of compound 6-a

Figure 112016053186677-pat00034

200 ml of a 50% sodium hydroxide aqueous solution was slowly added to a solution of 20.0 g (120.32 mmol) of fluorene and 7.76 g (24.06 mmol) of tetrabutylammonium bromide in 200 ml of toluene. After the temperature of the mixture was raised to 40 占 폚, 70.61 g (448.54 mmol) of 1-bromo-3-chloropropane was diluted in 80 ml of toluene and slowly added dropwise to the mixture. The mixture was stirred at 40 < 0 > C for 5 hours. After 300 ml of ice distilled water was poured slowly, the reaction was terminated, and 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: 10) to obtain 27.41 g (yield: 91%) of the compound 6-a

1 H-NMR (δ ppm: CDCl 3): 0.35 (6H, t), 1.05 (4H, m), 2.05 (4H, t), 7.28-7.39 (6H, m), 7.68 (2H, d)

Step 2. Preparation of compound 6-c

Figure 112016053186677-pat00035

Compound 6-b was prepared in the same manner as in step 1 of Example 1, except that 6-a was used instead of diphenylsulfan. 40 ml of acetic acid and 80 ml of acetic anhydride were mixed, and 10.74 g (46.20 mmol) of copper nitrate hydrate was added thereto, followed by stirring at room temperature for 10 minutes. 15.0 g (44.00 mmol) of 6-b was dissolved in 20 ml of acetic acid and then slowly added dropwise. After stirring at room temperature for 2 hours, the solution was slowly poured into 200 ml of ice distilled water. The precipitated solid was filtered and dried to obtain 14.94 g (88%) of compound 6-c.

1 H-NMR (δ ppm: CDCl 3): 0.40 (6H, t), 1.08 (4H, m), 2.10 (4H, t), 2.25 (2H, t), 3.48 (2H, t), 7.72-7.80 (1H, d), 7.88-8.05 (3H, m), 8.32-8.43 (2H, m)

Step 3. Preparation of compound 6

Figure 112016053186677-pat00036

Compound 6-d was prepared in the same manner as in the step 2 of Example 1, except that 6-c was used instead of 1-b. Compound 6-e was prepared in the same manner except that -d was used. 3.89 g (Yield: 71%) of Compound 6 was obtained in the same manner as in Step 2 of Example 2, except that 6-e was used instead of 3-d.

1 H-NMR (δ ppm: CDCl 3): 0.42 (6H, t), 1.07 (4H, m), 2.12 (4H, t), 2.28-2.42 (7H, m), 4.14-4.25 (4H, m) (2H, d), 5.25-5.32 (2H, d), 5.91-5.99 (2H, m), 7.76-7.85 (1H, d), 7.90-8.08 (3H, m), 8.35-8.45 2H, m)

 (Example 4) Preparation of Compound 8

Figure 112016053186677-pat00037

Figure 112016053186677-pat00038

A compound 8-a was prepared in the same manner as in the step 3 of Example 3, except that carbazole was used in place of the fluorene. In the same manner as in the steps 2 to 3 of Example 3, 4.55 g (Yield: 66%).

1 H-NMR (δ ppm: CDCl 3): 0.51 (3H, t), 2.04 (2H, m), 2.25-2.39 (7H, m), 4.11-4.20 (4H, m), 4.44 (2H, t) (2H, d), 5.20-5.29 (2H, d), 5.85-5.95 (2H, m), 7.45-7.56 (2H, d), 8.22-8.33 1H, < / RTI > s), 8.91-8.97 (1H, s)

(Example 5) Preparation of Compound 10

Step 1. Preparation of compound 10

Figure 112016053186677-pat00039

Except that 10-d was used in Step 3 of Example 2, the compound 10-e was prepared in the same manner except that 10-e was used in Step 4 of Example 2 4.69 g (yield 81%) of Compound 10 was obtained

1 H-NMR (δ ppm: CDCl 3): 1.45-1.62 (2H, m), 1.70-1.91 (8H, m), 2.23-2.39 (9H, m), 4.13-4.20 (4H, s), 6.00- (2H, m), 7.81-8.02 (2H, m), 7.78-7.83 (1H,

(Example 6) 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 15,000 g / mol, acid value 100 KOH mg / g), green pigment dispersion (CI Pigment Green 7, 20 wt% in PGMEA) , 10 g of dipentaerythritol hexaacrylate, 0.5 g of the photoactive compound prepared in Example 1, 0.1 g of pentaerythritol tetrakis 3-mercaptobutyrate, 0.1 g of 2-methacryloxypropyltrimethoxysilane, And 49.5 g of propylene glycol monomethyl ether acetate (PGMEA) were successively mixed and 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 90 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 90 seconds, followed by exposure at 365 nm, post-baking (post-baking) at 220 for 30 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 60 minutes for 10 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 7-10) Preparation of photoresist composition

Except that 0.5 g of the photoactive compound prepared in each of Examples 2 to 5 was used in place of the photoactive compound prepared in Example 1, the photoresist composition was prepared in the same manner as in Example 6, After the photoresist composition was prepared by the method of Example 6, its performance such as sensitivity, residual film ratio, chemical resistance and developability was measured and the results are shown in Table 1 below.

(Comparative Example 1) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 6 except that 0.5 g of OXE-02 (product of BASF, refer to the following structure) was used instead of the photoactive compound prepared in Example 1, 6, the performance of the photoresist composition such as sensitivity, residual film ratio, chemical resistance and developability was measured. The results are shown in Table 1 below.

(OXE-02 structure)

Figure 112016053186677-pat00040

Example Sensitivity
(mJ / cm 2 ) Residual film ratio
(%) Chemical resistance Developability Example 6 40 91 ○ ○ Example 7 40 91 ○ ○ Example 8 35 92 ○ ○ Example 9 30 94 ○ ○ Example 10 35 92 ○ ○ Comparative Example 1 50 87 △ X

As shown in Table 1, it can be seen that the photoresist composition containing the photoactive compound according to the present invention has a much higher sensitivity than the photoresist composition of the comparative example, and has excellent physical properties such as residual film ratio, chemical resistance and developability .

Claims (10)

A photoactive compound having an unsaturated group represented by the following formula (1);
[Chemical Formula 1]
Figure 112017065691076-pat00041

In the formula (1)
Ar 1 to Ar 3 are each independently hydrogen, -SR 11, -NR 12 R 13 , (C6-C30) aryl and (C3-C30) heteroaryl or more selected from selected from Ar 1 to Ar 3 are connected to each other It is can form a ring, wherein R 11 to R 13 are each independently hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl Or (C3-C30) heteroaryl;
Ar 4 is a single bond or (C1-C30) alkylene;
R 1 is hydrogen, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;
R 2 is (C 2 -C 30) alkenyloxy, (C 2 -C 30) alkynyloxy or -OL 1 -OC (═O) -R 14 , R 3 is (C 6 -C 30) aryl, heteroaryl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C2-C30) alkenyloxy, (C2-C30) alkynyloxy or -OL 1 -OC (= O) -R 14 , and , R 14 is (C 2 -C 30) alkenyl, (C 2 -C 30) alkynyl, R 2 and R 3 may be connected to each other to form a ring, L 1 is (C 1 -C 30) ;
n is an integer of 0 or 1;
Wherein Ar 1 to Ar 3 of the aryl, heteroaryl and the ring, the R 1 alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl, alkenyl of R 2 and R 3, alkynyl or rings are independently (C1, respectively (C3-C30) alkenyl, (C2-C30) alkynyl, (C3-C30) cycloalkyl, (C3- C30) heterocycloalkyl, (C6- heteroaryl, cyano, nitro, -CR 24, -OR 21, -SR 22, -NR 21 R 22, -C (= O) R 23, -C (= O) OR 23, -C (= O) NR 21 R 22 and -L 2 -P (= O) (OR 21 ) (OR 22 ), and R 21 To R 23 are each independently selected from hydrogen, heavy hydrogen (deuterium), (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C3-C30) cycloalkyl (C1-C30) alkyl , (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, (C1-C30) alkyl (C6-C30) aryl or (C3-C30) heteroaryl, wherein R 24 is a halogen, wherein L 2 is an alkylene single bond or a (C1-C30), wherein said heterocycloalkyl and heteroaryl is B, N, O, S, P (= O), one or more heteroatoms selected from Si and P Atoms.] The method according to claim 1,
A photoactive compound represented by the following formula (2);
(2)
Figure 112016053186677-pat00042

In the formula (2)
Ar 1 and Ar 2 are each independently selected from hydrogen, -SR 11 , (C 6 -C 20) aryl and (C 3 -C 20) heteroaryl,
Figure 112016053186677-pat00043
,
Figure 112016053186677-pat00044
or
Figure 112016053186677-pat00045
A can form a ring, wherein R 11 is (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl or (C3-C20) heteroaryl, and wherein R 31 to R 36 are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl, (C3-C20) heteroaryl, cyano, nitro or -L 2 -P (= O) ( oR 21) (oR 22) a, wherein L 2 is a single bond or alkylene (C1-C30), wherein R 21 And R 22 are each independently (C 2 -C 30) alkenyl or (C 2 -C 30) alkynyl;
Ar 4 is a single bond or (C 1 -C 20) alkylene;
n is an integer of 0 or 1;
R 1 is hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) heteroaryl;
R 2 is (C 2 -C 20) alkenyloxy or (C 2 -C 20) alkynyloxy, R 3 is (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, -C20) alkynyl, (C2-C20) alkenyloxy, (C2-C20) alkynyloxy or -OL 1 -OC (= O) and -R 14, wherein R 14 is (C2-C20) alkenyl, (C2-C20) alkynyl, R 2 and R 3 may be connected to each other to form a ring, L 1 is (C 1 -C 20) alkylene, the ring is (C 1 -C 20) C20) alkenyl, (C2-C20) alkynyl, (C3-C20) cycloalkyl and (C3-C20) heterocycloalkyl. The method according to claim 1,
R 2 is (C 2 -C 7 ) alkenyloxy, (C 2 -C 7 ) alkynyloxy or -OL 1 -OC (═O) -R 14 and R 3 is (C 6 -C 20) ) heteroaryl, (C2-C7) alkenyl, (C2-C7) alkynyl, (C2-C7) alkenyloxy, (C2-C7) alkynyloxy or -OL 1 -OC (= O) -R 14 and, L 1 is (C1-C7) alkylene, wherein R 14 is (C2-C7) alkenyl, (C2-C7), and alkynyl, wherein R 2 and R 3 are connected to
Figure 112016053186677-pat00046
or
Figure 112016053186677-pat00047
A can form a ring, wherein R 41 and R 42 are each independently hydrogen, (C2-C7) alkenyl, (C2-C7) alkynyl, (C3-C20) cycloalkyl or (C3-C20) heteroaryl A photoactive compound that is a cycloalkyl. The method according to claim 1,
And Ar < 4 > is (C1-C7) alkylene. The method according to claim 1,
A photoactive compound selected from the following structures;
Figure 112016053186677-pat00048

Figure 112016053186677-pat00049

Figure 112016053186677-pat00050
 A photopolymerization initiator composition comprising a photoactive compound according to claim 1. A photoresist composition comprising a photoactive compound according to claim 1 and a colorant. 8. The method of claim 7,
Wherein the photoresist composition further comprises a photosensitizer comprising a thiol group or a silyl group. A color filter comprising the photoresist composition according to claim 7. A black matrix comprising the photoresist composition according to claim 7.
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