KR101821674B1 - Triazine derivatives, photopolymerization initiator and photoresist composition containing the same - Google Patents
Triazine derivatives, photopolymerization initiator and photoresist composition containing the same Download PDFInfo
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- 0 CCC*(C(C(C)(CC)C(*)=*OC(*)=O)=O)N Chemical compound CCC*(C(C(C)(CC)C(*)=*OC(*)=O)=O)N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/28—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having nitrogen atoms of imino groups acylated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- 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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Abstract
The present invention relates to a novel triazine derivative, a photopolymerization initiator comprising the same, and a photoresist composition. The triazine derivative according to the present invention has oxime ester groups and triazine groups in one molecule at the same time, It is possible to provide a photopolymerization initiator composition and a photoresist composition which can not only effectively absorb light but can realize high sensitivity, heat resistance and chemical resistance.
Description
The present invention relates to a triazine derivative, a photopolymerization initiator comprising the same and a photoresist composition, and more particularly, to a novel oxime ester triazine derivative having oxime ester group and triazine group together, a photopolymerization initiator containing the same, will be.
The photopolymerization initiator can generate a radical active species by the irradiated light to cause a photopolymerization reaction of the polycondensation monomer, They can be selectively cured to form various patterns. Therefore, they are used in photocurable ink, photosensitive printing plate, various photoresists, and the like. As a photopolymerization initiator having such properties, various kinds of compounds such as acetophenone derivatives, oxime ester derivatives, triazine derivatives, benzophenone derivatives, bimidazole derivatives and acylphosphine oxide derivatives are known, and most of them are used Examples of the photopolymerization initiator include acetophenone derivatives, oxime ester derivatives, and triazine derivatives. Acetophenone derivatives have good color characteristics and good solubility and are relatively inexpensive. However, in order to obtain sufficient sensitivity, the residual film ratio is lowered, which may cause liquid crystal contamination, since 3% or more, or even 10% Concentration of the composition, particularly the black photosensitive composition, has a weak sensitivity, and there is a problem that desorption of the pattern is seriously occurred when the composition is used alone. The oxime ester derivative has low coloring and high transparency and is excellent in stability and compatibility in the composition but is not efficient in absorbing UV light source and has a problem that the process time is prolonged. When the concentration of the pigment is high or the thickness of the coating film is 2.5 It is still difficult to form a fine pattern because the curing degree of the thick film is not sufficiently satisfied, and the formed pattern can not satisfy the CD (critical dimension) and the mechanical strength required in the product (Patent Documents 1 and 2). Further, halomethyltriazine derivatives which are decomposed by light irradiation to generate halogen radicals in the triazine derivatives are known to have good sensitivity to a UV light source as compared with the above-mentioned photopolymerization initiators, but they have a high crystallinity, And tends to be rapidly crystallized in the film (Patent Document 3).
In order to solve the problems as described above, there is a demand for a new photopolymerization initiator which has characteristics such as higher sensitivity, excellent thermal stability and storage stability, and can meet cost reduction effect and industrial field demand.
Thus, the present applicant has found that oxime ester triazine derivatives which efficiently absorb a UV light source and can form radicals with a high conversion ratio and are excellent in high-temperature process characteristics with improved thermal stability, a photopolymerization initiator containing the same, The present invention has been completed to provide a resist composition.
An object of the present invention is to provide a novel triazine derivative having high sensitivity, heat resistance and chemical resistance as well as capable of effectively absorbing ultraviolet light as compared with conventional photopolymerization initiators by having oxime ester groups and triazine groups in one molecule simultaneously .
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 small amount of use.
The present invention provides a novel triazine derivative represented by the following general formula (1).
[Chemical Formula 1]
In the formula (1)
L 1 and L 2 are each independently a single bond, (C3-C30) heteroarylene or (C6-C30) arylene;
Z 1 is -C (= O) -, -O-, -S-, -S (= O) -, -SO 2 - or -Se-;
R 1 and R 2 are each independently selected from the group consisting of hydrogen, deuterium, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C 6 -C 30) C30) heteroaryl, nitro (-NO 2), cyano (-CN), -C (= O ) R 21, -C (= O) oR 22 or
p is an integer of 0 or 1;
Wherein L 1 and heteroarylene, arylene of L 2 and the R 1, and alkyl of R 2, cycloalkyl, heterocycloalkyl, aryl, heteroaryl 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) may further be substituted with one or more substituents selected from the group consisting of NR b R c, and P (= O) (OR a ) (OR b) 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.
The present invention provides a photopolymerization initiator composition and a photoresist composition comprising at least one selected from the triazine derivatives represented by the above formula (1).
In addition, the present invention can provide a color filter or a black matrix having an excellent residual film ratio, mechanical strength, heat resistance, chemical resistance, and resistance to development with high sensitivity by effectively absorbing ultraviolet rays using the triazine derivative described above. 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 triazine derivative according to the present invention has both a oxime ester group and a triazine group in the molecule and thus has superior sensitivity than conventional photopolymerization initiators and also contains a substituent connected with heteroarylene or arylene linked by a hetero atom, Can have improved compatibility with colorants or binder resins.
The photoresist composition containing the triazine derivative having high sensitivity according to the present invention can remarkably improve the polymerization and curing reaction speed of the polymerizable compound having unsaturated bonds by irradiation with light, By controlling the polymerization and curing reaction rates appropriately, desired physical properties can be realized.
In addition, since the photoresist composition according to the present invention can realize excellent reactivity even at a low exposure dose, remarkably improved physical properties can be realized even in the case of a black matrix in which a high colorant is used. In addition, by reacting with a photosensitizer containing a thiol group, physical properties such as a residual film ratio, mechanical strength, chemical resistance and developability can be remarkably improved, and a photopolymerization initiator can be obtained from an exposure and post- The outgassing that can occur can be minimized and the defect rate can be minimized.
The novel triazine derivatives according to the present invention, the photopolymerization initiator and the photoresist composition containing the triazine derivatives, and the photoresist composition containing the same are described below. However, unless otherwise defined in 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 attain the object of the present invention, the photoresist composition of the present invention can have improved optical sensitivity by simultaneously containing an oxime ester group and a triazine group, which may be a triazine derivative represented by the following general formula (1).
[Chemical Formula 1]
In the formula (1)
L 1 and L 2 are each independently a single bond, (C3-C30) heteroarylene or (C6-C30) arylene;
Z 1 is -C (= O) -, -O-, -S-, -S (= O) -, -SO 2 - or -Se-;
R 1 and R 2 are each independently selected from the group consisting of hydrogen, deuterium, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C 6 -C 30) C30) heteroaryl, nitro (-NO 2), cyano (-CN), -C (= O ) R 21, -C (= O) oR 22 or
p is an integer of 0 or 1;
Wherein L 1 and heteroarylene, arylene of L 2 and the R 1, and alkyl of R 2, cycloalkyl, heterocycloalkyl, aryl, heteroaryl 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) may further be substituted with one or more substituents selected from the group consisting of NR b R c, and P (= O) (OR a ) (OR b) 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.
The term "halogen" of the present invention means fluoro, chloro, bromo or iodo.
The term "alkyl" and any other substituents comprising the "alkyl" moiety of the present invention refer to hydrocarbon radicals that include both linear and branched forms, preferably (C1-C10) alkyl, a 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, and the like, but is not limited thereto.
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 "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.
The triazine derivative 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, wherein L 1 and L 2 each independently represent a single bond And the following structures, but are not limited thereto.
[In the above structure,
Z 11 to Z 14 are -S-, -O- or -Se-;
R 11 to R 19 are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 1 -C 10) thioxy, halogen or -CCl 3 .
In addition, the triazine derivative according to an embodiment of the present invention significantly improves the sensitivity and heat resistance to ultraviolet rays by introducing heteroarylene or arylene, which is connected to the triazine group through a linking group containing a hetero atom, between the oxime ester group and the triazine group . Also, it can react with a photosensitizer containing a thiol group to form a fine pattern with high adhesion to a substrate and high strength.
The triazine derivative according to an embodiment of the present invention is excellent in compatibility with a coloring agent, a binder resin and the like due to its high solubility, and in view of minimizing problems such as deposition after coating and desorption of a pattern on a substrate, L 1 - (Z 1 ) p -L 2 - can be selected from the following structures, but is not limited thereto.
[In the above structure,
Z 1 , Z 11 and Z 12 are each independently -S- or -O-;
R 11 to R 19 are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 1 -C 10) thioxy, halogen or -CCl 3 .
The triazine derivative according to an embodiment of the present invention preferably has a structure represented by the following formula (2) or (3) in view of being capable of minimizing contamination due to by-products generated during the steps of exposure and post- But it is not limited thereto.
(2)
(3)
In the formulas (2) and (3)
Z 1 and Z 11 are -S- or -O-;
R 11 to R 14 are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 1 -C 10) thioxy, halogen or -CCl 3 ;
R 1 and R 2 are each independently selected from the group consisting of hydrogen, deuterium, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C 6 -C 30) C30) heteroaryl, nitro (-NO 2), cyano (-CN), -C (= O ) R 21, -C (= O) oR 22 or
Alkyl of said R 1 and R 2, cycloalkyl, heterocycloalkyl, aryl, heteroaryl 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 ), 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.
The triazine derivative represented by the formula (1) according to an embodiment of the present invention can be used not only in high solubility but also in a small amount due to its high sensitivity, in view of realizing excellent properties such as retention rate, mechanical strength, chemical resistance and developability But the present invention is not limited thereto.
The triazine derivative 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 triazine derivative.
The present invention also provides a photoresist composition comprising the triazine derivative.
The photoresist composition according to the present invention includes a binder resin, a colorant, and a triazine derivative. The triazine derivative may be contained in an amount of 0.01 to 15% by weight, preferably 0.01 to 10% by weight, 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 2,000 to 300, 000 g / mol and a dispersion degree of 1.0 to 10.0 in terms of high compatibility with the triazine 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 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. In this case, the photosensitizer preferably contains a thiol group, and the photosensitizer containing a thiol group can rapidly react with the triazine derivative according to the present invention to achieve sensitivity to significantly enhanced light, The residual film ratio and developability of the produced color filter, black matrix and the like can be significantly improved.
The photo sensitizer having high reactivity with the triazine 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 triazine 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, triazine derivative, binder resin and 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 is excellent in developability, durability, and chemical resistance with high brightness and high contrast ratio by using at least one triazine derivative represented by the above formula (2) and A color filter 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).
Example 1 Preparation of 2,4-Bis (trichloromethyl) -6- (4'-pentanoylacetoxime-biphenyl) -s-triazine (Compound 1)
Step 1. Preparation of 2,4-Bis (trichloromethyl) -6- (4'-pentylbiphenyl) -s-triazine (1b)
Aluminum bromide (1.06 g, 4.01 mmol) was added to a solution of 4'-pentyl-4-biphenylcarbonitrile 1a (10.0 g, 40.10 mmol) in trichloroacetonitrile (92.64 g, 641.64 mmol). Hydrogen chloride gas dried through a dip tube was poured into the mixture at 0 ° C for 3 hours and stirred at room temperature (23 ° C) for 12 hours. 2,4,6-tris (trichloromethyl) -s-triazine was dissolved and removed by using n-hexane to crystallize the product 1b (14.67 g, yield = 68%).
1 H-NMR (δ ppm: CDCl 3): 8.75 ~ 8.72 (2H, d, ArH), 7.80-7.77 (2H, d, ArH), 7.61-7.59 (2H, d, ArH), 7.33-7.30 (2H , d, ArH), 2.75 ( 2H, t, CH 2), 1.66 (2H, m, CH 2), 1.34 (4H, m, CH 2 -CH 2), 0.91 (3H, t, CH 3).
Step 2. Preparation of 2,4-Bis (trichloromethyl) -6- (4'-pentanoyl-biphenyl) -s-triazine (1c)
The compound 1b (12.0 g, 22.30 mmol) synthesized in the above reaction was dissolved in 100 mL of methylene chloride and then chromium oxide (0.223 g, 2.23 mmol) and 70% t-butyl peroxide (20.09 g, 156.09 mmol) The mixture was stirred at room temperature for 24 hours. The mixture was extracted with water and methylene chloride. The organic layer was dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain the product 1c (10.71 g, yield = 87%).
1 H-NMR (δ ppm: CDCl 3): 8.79 ~ 8.76 (2H, d, ArH), 8.09-8.06 (2H, d, ArH), 7.85-7.83 (2H, d, ArH), 7.79-7.77 (2H , d, ArH), 2.95 ( 2H, t, CH 2), 1.72 (2H, m, CH 2), 1.41 (2H, m, CH 2), 0.93 (3H, t, CH 3).
Step 3. Preparation of 2,4-Bis (trichloromethyl) -6- (4'-pentanoyloxime-biphenyl) -s-triazine (1d)
The synthesized compound 1c (10.0 g, 18.11 mmol) was dissolved in tetrahydrofuran (60 mL) under nitrogen atmosphere, and then 15 mL of 4N hydrogen chloride (1,4-dioxane) and isopentyl nitrite (2.54 g, 21.7 mmol) Respectively. After stirring at room temperature for 5 hours, the reaction solution was slowly poured into 150 mL of distilled water to complete the reaction. The solid precipitate was dissolved in ethyl acetate and washed sequentially with saturated sodium hydrogencarbonate and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the organic solvent was removed under reduced pressure to obtain a pale yellow solid compound 1d (7.57 g, yield = 72%).
1 H-NMR (δ ppm: CDCl 3): 8.79 ~ 8.76 (2H, d, ArH), 8.09 (1H, s, NOH), 7.85-7.83 (2H, d, ArH), 7.78-7.69 (4H, m , ArH), 2.65 (2H, t, -N = CCH 2), 1.68- 1.41 (4H, m, CH 2 -CH 2), 0.92 (3H, t, CH 3).
Step 4. Preparation of 2,4-Bis (trichloromethyl) -6- (4'-pentanoylacetoxime-biphenyl) -s-triazine (1)
Acetic anhydride (1.26 g, 12.39 mmol) was added to a solution of Compound 1d (6.0 g, 10.32 mmol) obtained in the above reaction and 30 mL of methylene dichloride in triethylamine (1.46 g, 14.45 mmol) Lt; / RTI > The reaction product was extracted with water and methylene dichloride, the organic layer was separated, the residual water was removed with sodium sulfate, and the solvent was removed under reduced pressure. The resulting organic substance was purified by column chromatography to obtain Compound (1) (5.72 g, yield = 89%).
1 H-NMR (δ ppm: CDCl 3): 8.77 ~ 8.74 (2H, d, ArH), 7.91-7.79 (4H, d & d, ArH), 7.74-7.71 (2H, d, ArH), 2.63 (2H, t , -N = CCH 2), 2.43 (3H, s, O = CCH 3), 1.68- 1.41 (4H, m, CH 2 -CH 2), 0.92 (3H, t, CH 3).
Example 2 Preparation of 2,4-Bis (trichloromethyl) -6- [4 '- (4 "-1,2-propanedion-2-acetoxime phenylthio) phenyl] -s-
Step 1. Preparation of 4- (4'-propionylphenylthio) benzonitrile (2b)
4-fluoropropionone (13.28 g, 13.28 mmol) and potassium carbonate (20.44 g, 147.95 mmol) were added to a solution of 4-mercaptobenzonitrile 2a (10 g, 73.97 mmol) in 70 mL of DMF. The mixture was stirred at 130 ° C for 20 hours and then cooled to room temperature. 100 mL of water and 200 mL of methylene chloride were added to the reaction solution, and the organic material was separated, dried using sodium sulfate, Respectively. 2b was purified by column chromatography using hexane / ethyl acetate = 4/1 solution (10.66 g, yield = 54%).
1 H-NMR (δ ppm: CDCl 3): 7.96-7.94 (2H, d, ArH), 7.58-7.56 (2H, d, ArH), 7.48-7.46 (2H, d, ArH), 7.35-7.33 (2H , d, ArH), 2.96 ( 2H, q, CH 2), 1.19 (3H, t, CH 3).
Step 2. Preparation of 2,4-Bis (trichloromethyl) -6- (4'-propionylphenylthio) phenyl-s-triazine (2c)
Aluminum bromide (0.978 g, 3.66 mmol) was added to a solution of Compound 2b (9.8 g, 36.65 mmol) synthesized in the above reaction in trichloroacetonitrile (84.67 g, 586.49 mmol). Hydrogen chloride gas dried through a dip tube was poured into the mixture at 0 ° C for 3 hours and stirred at room temperature for 12 hours. 2,4,6-Tris (trichloromethyl) -s-triazine was dissolved and removed by using n-hexane to crystallize the product, 2c (11.41 g, yield = 56%).
1 H-NMR (δ ppm: CDCl 3): 8.63-8.61 (2H, d, ArH), 7.95-7.93 (2H, d, ArH), 7.52-7.46 (4H, m, ArH), 2.95 (2H, q , CH 2), 1.18 (3H , t, CH 3).
Step 3. Preparation of 2,4-Bis (trichloromethyl) -6- [4 '- (1,2-propanedion-2-oxime) phenylthio) phenyl] -s-
The synthesized compound 2c (10.5 g, 18.88 mmol) was dissolved in 60 mL of tetrahydrofuran under nitrogen atmosphere, 15 mL of 4N hydrogen chloride (1,4-dioxane) and isopentyl nitrite (2.65 g, 22.65 mmol) Respectively. After stirring at room temperature for 5 hours, the reaction solution was slowly poured into 150 mL of distilled water to complete the reaction. The solid precipitate was dissolved in ethyl acetate and washed sequentially with saturated sodium hydrogencarbonate solution and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the organic solvent was removed under reduced pressure to obtain a pale yellow solid compound 2d (8.06 g, yield = 73%).
1 H-NMR (δ ppm: DMSO-D 6): 11.40 (1H, s, NOH), 8.47-8.45 (2H, d, ArH), 7.77-7.75 (2H, d, ArH), 7.52-7.46 (4H , m, ArH), 2.06 ( 3H, s, CH 3).
Step 4. Preparation of 2,4-Bis (trichloromethyl) -6- [4 '- (1,2-propanedion-2-acetoxime) phenylthio) phenyl]
Acetic anhydride (1.04 g, 10.25 mmol) was added to a solution of Compound 2d (5.0 g, 8.54 mmol) obtained in the above reaction and 30 mL of methylene dichloride in triethylamine (1.21 g, 11.96 mmol) Lt; / RTI > The reaction product was extracted with water and methylene dichloride, the organic layer was separated, the residual water was removed with sodium sulfate, and the solvent was removed under reduced pressure. The obtained organic substance was purified by column chromatography to obtain Compound 2 (4.6 g, yield = 86%).
1 H-NMR (δ ppm: CDCl 3): 8.58-8.56 (2H, d, ArH), 7.79-7.77 (2H, d, ArH), 7.53-7.52 (2H, d, ArH), 7.38-7.36 (2H , d, ArH), 2.42 ( 3H, s, O = CCH 3), 2.04 (3H, s, -N = CCH 3).
Example 3 Preparation of 2,4-Bis (trichloromethyl) -6- [4 '- (4 "-1,2-propanedion-2-acetoxime phenoxy) phenyl] -s-
Step 1. Preparation of 4- (4'-propionyl-phenoxy) benzonitrile (3b)
4-fluoropropionone (15.07 g, 99.06 mmol) and potassium carbonate (23.20 g, 167.90 mmol) were added to a solution of 4-hydroxybenzonitrile 3a (10.0 g, 83.95 mmol) in 100 mL of DMF. The mixture was stirred at 130 ° C for 20 hours and then cooled to room temperature. 100 mL of water and 200 mL of methylene chloride were added to the reaction solution, and the organic material was separated, dried using sodium sulfate, Respectively. 3b was purified by column chromatography using hexane / ethyl acetate = 4/1 solution (11.18 g, yield = 53%).
1 H-NMR (δ ppm: CDCl 3): 8.03-8.01 (2H, d, ArH), 7.66-7.64 (2H, d, ArH), 7.10-7.07 (4H, m, ArH), 2.92 (2H, q , CH 2), 1.14 (3H , t, CH 3).
Step 2. Preparation of 2,4-Bis (trichloromethyl) -6- (4'-propionyl-phenoxy) phenyl-s-triazine (3c)
Aluminum bromide (1.08 g, 4.06 mmol) was added to a solution of compound 3b (10.2 g, 40.59 mmol) synthesized in the above reaction in trichloroacetonitrile (98.77 g, 649.47 mmol). Hydrogen chloride gas dried through a dip tube was poured into the mixture at 0 ° C for 3 hours and stirred at room temperature for 12 hours. 2,4,6-Tris (trichloromethyl) -s-triazine was dissolved and removed by using n-hexane to crystallize the product 3c (12.93 g, yield = 59%).
1 H-NMR (δ ppm: CDCl 3): 8.71-8.69 (2H, d, ArH), 8.01-7.99 (2H, d, ArH), 7.20-7.13 (4H, m, ArH), 2.93 (2H, q , CH 2), 1.15 (3H , t, CH 3).
Step 3. Preparation of 2,4-Bis (trichloromethyl) -6- [4 '- (1,2-propanedion-2-oxime) phenoxy) phenyl] -s-
The synthesized compound 3c (10.0 g, 18.51 mmol) was dissolved in 60 mL of tetrahydrofuran under nitrogen atmosphere, 15 mL of 4N hydrogen chloride (1,4-dioxane) and isopentyl nitrite (2.60 g, 22.22 mmol) Respectively. After stirring at room temperature for 5 hours, the reaction solution was slowly poured into 150 mL of distilled water to complete the reaction. The solid precipitate was dissolved in ethyl acetate and washed sequentially with saturated sodium hydrogencarbonate solution and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the organic solvent was removed under reduced pressure to obtain a pale yellow solid compound 3d (7.90 g, yield = 75%).
1 H-NMR (δ ppm: DMSO-D 6): 11.22 (1H, s, NOH), 8.56-8.54 (2H, d, ArH), 7.74-7.72 (2H, d, ArH), 7.29-7.15 (4H , m, ArH), 2.08 ( (3H, s, CH 3).
Step 4. Preparation of 2,4-Bis (trichloromethyl) -6- [4 '- (1,2-propanedion-2-benzoxime) phenoxy) phenyl]
Benzoyl chloride (1.77 g, 12.65 mmol) was added to a solution of compound 3d obtained in the above reaction (6.0 g, 10.54 mmol) and triethylamine (1.49 g, 14.76 mmol) in 40 mL of methylene dichloride. Lt; / RTI > The reaction product was extracted with water and methylene dichloride, the organic layer was separated, the residual water was removed with sodium sulfate, and the solvent was removed under reduced pressure. The obtained organic substance was purified by column chromatography using a 4/1 solution of hexane / ethyl acetate to give compound (3) (5.89 g, yield = 83%).
1 H-NMR (δ ppm: CDCl 3): 8.56-8.54 (2H, d, ArH), 8.04-8.01 (2H, d, ArH), 7.74-7.15 (9H, m, ArH), 2.40 (3H, s , O = CCH 3), 2.07 ((3H, s, CH 3).
Example 4 Preparation of 2,4-Bis (trichloromethyl) -6- [4 '- (4 "-1,2-propanedion-2-acetoxime phenoxy) phenyl] -s-
Step 1. Preparation of 2,4-Bis (trichloromethyl) -6- (2'-propionylthiophen-5-yl) -s-triazine (4b)
Aluminum bromide (1.61 g, 6.05 mmol) was added to a solution of 5-Cyano-2-propionylthiophene 4a (10.0 g, 60.53 mmol) in trichloroacetonitrile (131.08 g, 907.93 mmol). Hydrogen chloride gas, which had been dried through a dip tube, was poured into the mixture at 0 ° C for 5 hours and stirred at room temperature for 12 hours. 2,4,6-Tris (trichloromethyl) -s-triazine was dissolved and removed by using n-hexane to crystallize the product 4b (18.41 g, yield = 67%).
1 H-NMR (δ ppm: CDCl 3): 8.86 (1H, d, ArH), 8.22 (1H, d, ArH), 2.93 (2H, s, CH 2), 1.21 (3H, t, CH 3)
Step 2. Preparation of 2,4-Bis (trichloromethyl) -6- (2'-propionyloxime-thiophen-5-yl) -s-triazine (4c)
The synthesized compound 4b (15.0 g, 33.04 mmol) was dissolved in 80 mL of tetrahydrofuran under a nitrogen atmosphere, 20 mL of 4N hydrogen chloride (1,4-dioxane) and isopentyl nitrite (4.64 g, 39.64 mmol) Respectively. After stirring at room temperature for 5 hours, the reaction solution was slowly poured into 150 mL of distilled water to complete the reaction. The solid precipitate was dissolved in ethyl acetate and washed sequentially with saturated sodium hydrogencarbonate solution and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the organic solvent was removed under reduced pressure to obtain a pale yellow solid compound 4c (11.96 g, yield = 75%).
1 H-NMR (δ ppm: CDCl 3): 8.87 (1H, d), 8.32 (1H, s, NOH)), 8.25 (1H, d, ArH), 2.28 (3H, s, CH 3)
Step 3. Preparation of 2,4-Bis (trichloromethyl) -6- (2'-propionylacetoxime-thiophen-5-yl) -s-triazine (4)
Acetic anhydride (1.52 g, 14.90 mmol) was added to a solution of compound 4c (6.0 g, 12.42 mmol) obtained in the above reaction and triethylamine (1.76 g, 17.39 mmol) in 40 mL of methylene dichloride. Lt; / RTI > The reaction product was extracted with water and methylene dichloride, the organic layer was separated, the residual water was removed with sodium sulfate, and the solvent was removed under reduced pressure. The obtained organic substance was purified using column chromatography (hexane / ethyl acetate = 3/1) to obtain Compound (4) (5.80 g, yield = 89%).
1 H-NMR (δ ppm: CDCl 3): 8.88 (1H, d), 8.26 (1H, d), 2.48 (3H, s, O = CCH 3), 2.31 (3H, s, N = CCH 3)
(Example 5) 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 triazine derivative 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 6) Preparation of photoresist composition
A photoresist composition was prepared in the same manner as in Example 5 except that 0.5 g of the triazine derivative prepared in Example 2 was used instead of the triazine derivative prepared in Example 1, 5, 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.
(Example 7) Preparation of photoresist composition
A photoresist composition was prepared in the same manner as in Example 5 except that 0.5 g of the triazine derivative prepared in Example 3 was used instead of the triazine derivative prepared in Example 1, 5, 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.
(Example 8) Preparation of photoresist composition
A photoresist composition was prepared in the same manner as in Example 5 except that 0.5 g of the triazine derivative prepared in Example 4 was used instead of the triazine derivative prepared in Example 1, 5, 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.
(Comparative Example 1) Preparation of photoresist composition
Except that 0.5 g of TAZ-110 (Midori Kagaku Co., Ltd., refer to the following structure) was used in place of the triazine derivative prepared in Example 1, and the photoresist composition was prepared in the same manner as in Example 5 The sensitivity, residual film ratio, chemical resistance and developability of the photoresist composition were measured by the method of Example 5, and the results are shown in Table 1 below.
(TAZ-110 structure)
(Comparative Example 2) Preparation of photoresist composition
A photoresist composition was prepared in the same manner as in Example 5 except that 0.5 g of OXE-02 (BASF product, see structure below) was used instead of the triazine derivative prepared in Example 1, The properties of the photoresist composition such as sensitivity, residual film ratio, chemical resistance and developability were measured by the method of Example 5, and the results are shown in Table 1 below.
(OXE-02 structure)
(Comparative Example 3) Preparation of photoresist composition
Except that a mixture of 0.25 g of OXE-02 (manufactured by BASF) and 0.25 g of TAZ-110 (Midori Kagaku) was used in place of the triazine derivative prepared in Example 1, After the composition was prepared, the performance of the photoresist composition such as sensitivity, residual film ratio, chemical resistance and developability was measured by the method of Example 5, and the results are shown in Table 1 below.
As shown in Table 1, the photoresist composition containing the triazine derivative 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 have.
Claims (11)
[Chemical Formula 1]
[Chemical Formula 1]
L 1 and L 2 are each independently (C 3 -C 30) heteroarylene or (C 6 -C 30) arylene;
Z 1 is -O-, -S- or -Se-;
R 1 and R 2 are each independently hydrogen, deuterium, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, or (C3-C30) Heteroaryl;
Wherein L 1 and heteroarylene of L 2, or arylene, and wherein R 1, and alkyl of R 2, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl are each independently (C1-C30) alkyl, (C3 (O) -C (O) O, S, P (O) -C (O) O- wherein the heterocycloalkyl and heteroaryl may be further substituted with one or more substituents selected from the group consisting of ), Si and P.
L < 1 > and L < 2 > each independently selected from the following structures;
[In the above structure,
Z 11 to Z 14 are -S- or -O-;
R 11 to R 19 are each independently hydrogen or (C 1 -C 10) alkyl.
Wherein -L 1 -Z 1 -L 2 - is selected from the following structures;
[In the above structure,
Z 1 , Z 11 and Z 12 are each independently -S- or -O-;
R 11 to R 19 are each independently hydrogen or (C 1 -C 10) alkyl.
A triazine derivative represented by the following formula (2);
(2)
In the formula (2)
Z 1 is -S- or -O-;
R 11 to R 14 are each independently hydrogen or (C 1 -C 10) alkyl;
R 1 and R 2 are each independently hydrogen, deuterium, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, or (C3-C30) Heteroaryl;
Alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl of each of R 1 and R 2 is independently selected from the group consisting of (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, and (C 3 -C 30) heterocycloalkyl And wherein said heterocycloalkyl and heteroaryl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P.
Wherein R 1 and R 2 are each independently hydrogen, deuterium, (C 1 -C 10) alkyl, or (C 6 -C 20) aryl.
A triazine derivative selected from the following structures;
Wherein the photoresist composition further comprises a photosensitizer comprising a thiol group.
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