WO2019216600A1 - Nouveau composé d'ester d'oxime et composition de résine photosensible le comprenant - Google Patents

Nouveau composé d'ester d'oxime et composition de résine photosensible le comprenant Download PDF

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WO2019216600A1
WO2019216600A1 PCT/KR2019/005284 KR2019005284W WO2019216600A1 WO 2019216600 A1 WO2019216600 A1 WO 2019216600A1 KR 2019005284 W KR2019005284 W KR 2019005284W WO 2019216600 A1 WO2019216600 A1 WO 2019216600A1
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group
unsubstituted
substituted
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compound
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PCT/KR2019/005284
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진성민
문봉석
강지승
홍원기
하민수
이규성
진상준
박노길
이현우
변우근
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주식회사 트리엘
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/63—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • 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
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the present invention relates to a novel oxime ester compound and a photoresist composition comprising the same, and more particularly, by absorbing UV and efficiently generating radicals, high transparency and high sensitivity can be realized, and outgas can be minimized.
  • the present invention relates to a novel oxime ester compound and a photoresist composition comprising the same.
  • a medium is required.
  • the medium is called a photoresist (PR).
  • Such a photoresist is a material that can selectively remove the lighted portion and the non-lighted portion during the subsequent development process by using the characteristic that the solubility in the developer is changed by receiving light of a specific wavelength.
  • photoresist removes the part selectively changed by light by using developer.
  • Positive resist is the case where the lighted area is melted well by developer, and vice versa. resist).
  • a photoresist composition is uniformly coated or coated on an insulating film or a conductive metal film formed on a substrate, and a mask having a predetermined shape is present.
  • the photoresist composition coated under the above is exposed and developed with an alkaline aqueous developer or the like to form a pattern of a desired shape.
  • the patterned photoresist film is used as a mask to dry or wet etch the metal film or the insulating film, and then the remaining photoresist film is removed to form a fine circuit on the substrate.
  • the photoresist composition is obtained by adding a photoinitiator to a polymerizable compound having an ethylenically unsaturated bond, and a photoinitiator having excellent sensitivity to a long wavelength UV light source is desired.
  • a photoinitiator having excellent sensitivity to a long wavelength UV light source is desired.
  • oxime ester compounds have been gradually used in photoresist compositions due to their relatively excellent photosensitive properties.
  • the oxime ester derivatives used in the prior arts have the advantages of excellent solubility and stability in the solvent used, but due to low photo-initiation efficiency and contamination of equipment due to outgassing during the exposure and heating processes, There is a problem of this shrinking.
  • the present invention relates to a photoresist composition which is developed with an alkaline developer used in a thin film display and is capable of forming a pattern with color resists, organic insulating films, liquid crystal alignment films, column spacers, UV overcoats, etc. of thin film display devices such as TFT-LCDs and OLEDs.
  • a photoresist composition containing a binder resin, a polyfunctional monomer having an ethylenically unsaturated bond, and a photoinitiator is preferred.
  • the sensitivity is low during the exposure process for pattern formation, so the amount of use of the photoinitiator must be increased or the exposure amount must be increased.
  • the contamination of the equipment due to the foreign matter generated after the decomposition of the photoinitiator and thereby the yield is reduced.
  • an object of the present invention is to substitute sulfide groups for fluorene, dibenzofuran, and dibenzothiophene, which have excellent solubility, to provide additional solubility due to excellent solubility in long wavelength UV light source and excellent solubility. It is possible to provide an oxime ester compound as a photoinitiator having a characteristic that can minimize the end group structure to minimize the outgas generation.
  • a second technical problem according to the present invention includes the oxime ester compound, by absorbing UV to efficiently generate radicals to provide a photoresist composition having high transparency, high sensitivity, and minimize the outgas There is a purpose.
  • the present invention provides a novel oxime ester compound represented by the following [Formula A] in order to provide a photoresist composition excellent in light sensitivity and excellent in heat resistance.
  • the substituent R ′ is hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted hetero atom, N, O, P, Si And C 3 -C 24 heteroaryl group having 1 to 3 atoms selected from S, substituted or unsubstituted C 1 -C 20 hydroxyalkyl group, substituted or unsubstituted C 7 -C 24 arylalkyl group And a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
  • M is 0 or 1
  • N is 1 or 2, and when n is 2, each R'-S is the same or different,
  • the substituents R 1 and R 2 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6
  • An aryl group of -C 30 a substituted or unsubstituted heteroaryl group of C 3 -C 24 having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms, a substituted or unsubstituted C Any one selected from a 1 -C 20 alkoxy group, a substituted or unsubstituted C 7 -C 24 arylalkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
  • the substituents R 5 to R 6 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6
  • An aryl group of -C 30 a substituted or unsubstituted heteroaryl group of C 3 -C 24 having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms, a substituted or unsubstituted C 1- C 20 alkoxy group, substituted or unsubstituted C 7 -C 24 arylalkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl A group, a substituted or unsubstituted C 6 -C 20 arylthionyl group, a substituted or unsubsti
  • X is any one selected from CR 3 R 4 , S, O,
  • the substituents R 3 and R 4 are the same or different, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or C 3 -C 24 heteroaryl group, unsubstituted or unsubstituted C 1 -C 20 alkoxy group, unsubstituted and having 1 to 3 atoms selected from hetero atoms as N, O, P, Si, and S Or an unsubstituted C 7 -C 20 arylalkyl group or a substituted or unsubstituted C 3 -C 20 cycloalkyl group, and the substituents R 3 and R 4 are bonded to each other to form an alicyclic or aromatic group. Can form a monocyclic or polycyclic ring,
  • K is an integer selected from 0 to 4-n, and when k is 2 or more, each R 6 is the same as or different from each other,
  • L is an integer selected from 0 to 3, and when l is 2 or more, each R 5 is the same as or different from each other,
  • 'Substituted' in 'substituted or unsubstituted' in [Formula A] is deuterium, cyano group, nitro group, halogen group, hydroxy group, C 1 -C 24 alkyl group, C 3 -C 20 cycloalkyl group, alkynyl group of C 1 -C 24 halogenated alkyl group, C 2 -C 24 alkenyl, C 2 -C 24 of, C 1 - 24 heterocyclic group in the alkyl group, C 6 -C 24 aryl, C 7 -C 24 Arylalkyl group, C 3 -C 24 heteroaryl group, C 3 -C 24 heteroarylalkyl group, C 1 -C 24 alkoxy group, C 1 -C 24 alkylamino group, C 6 -C 24 arylamino group Substituted with one or more substituents selected from the group consisting of C 3 -C 24 heteroarylamino group, C 1
  • the present invention also provides a photoresist composition comprising the oxime ester compound.
  • the photoresist composition comprising the novel oxime ester compound represented by [Formula A] according to the present invention can efficiently absorb UV to provide a high sensitivity photoresist composition, and in particular, at the time of high temperature crosslinking according to the prior art. Yield decreases due to foreign substances generated after the photoinitiator is decomposed, and the problem of decreased production due to increased exposure time due to increased exposure amount can be solved, and a photoresist composition having excellent sensitivity to a long wavelength UV light source can be provided. It can be effective.
  • the present invention provides an oxime ester compound represented by the above [Formula A].
  • the substituent R ′ is hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted hetero atom, N, O, P, Si And a C 3 -C 24 heteroaryl group having 1 to 3 atoms selected from S, a substituted or unsubstituted C 1 -C 20 hydroxyalkyl group, a substituted or unsubstituted C 7 -C 24 arylalkyl group , And any one selected from a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
  • M is 0 or 1
  • N is 1 or 2, and when n is 2, each R'-S is the same or different,
  • the substituents R 1 and R 2 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6
  • An aryl group of -C 30 a substituted or unsubstituted heteroaryl group of C 3 -C 24 having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms, a substituted or unsubstituted C Any one selected from a 1 -C 20 alkoxy group, a substituted or unsubstituted C 7 -C 24 arylalkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
  • the substituents R 5 to R 6 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6
  • An aryl group of -C 30 a substituted or unsubstituted heteroaryl group of C 3 -C 24 having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms, a substituted or unsubstituted C 1- C 20 alkoxy group, substituted or unsubstituted C 7 -C 24 arylalkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl A group, a substituted or unsubstituted C 6 -C 20 arylthionyl group, a substituted or unsubsti
  • X is any one selected from CR 3 R 4 , S, O,
  • the substituents R 3 and R 4 are the same or different, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or C 3 -C 24 heteroaryl group, unsubstituted or unsubstituted C 1 -C 20 alkoxy group, unsubstituted and having 1 to 3 atoms selected from hetero atoms as N, O, P, Si, and S Or an unsubstituted C 7 -C 20 arylalkyl group or a substituted or unsubstituted C 3 -C 20 cycloalkyl group, and the substituents R 3 and R 4 are bonded to each other to form an alicyclic or aromatic group. Can form a monocyclic or polycyclic ring,
  • K is an integer selected from 0 to 4-n, and when k is 2 or more, each R 6 is the same as or different from each other,
  • L is an integer selected from 0 to 3, and when l is 2 or more, each R 5 is the same as or different from each other,
  • the 'substituted' in 'substituted or unsubstituted' in [Formula A] is deuterium, cyano group, nitro group, halogen group, hydroxy group, C 1 -C 24 alkyl group, substituted or unsubstituted C 3 of the -C 20 cycloalkyl group, C 1 -C 24 halogenated alkyl group, C 2 -C 24 alkenyl group, C 2 -C 24 alkynyl group of, C 1 - 24 heterocyclic group, C 6 -C 24 aryl group, C 7 -C 24 arylalkyl group, C 3 -C 24 heteroaryl, C 3 -C 24 heteroaryl group, C 1 -C 24 alkoxy group, C 1 -C 24 in the alkyl group, C In the group consisting of 6 -C 24 arylamino group, C 3 -C 24 heteroarylamino group, C 1 -C 24 alkoxy group
  • a functional group including an oxime ester group is bonded to one benzene ring of fluorene, dibenzofuran or dibenzothiophene according to the kind of X in the formula (A).
  • the functional group including the oxime ester group includes substituents R 1 and R 2 , and may further have a carbonyl group at the benzene ring side.
  • oxime ester compound represented by the above [Formula A] is used as a photoresist composition, a structure in which sulfide is bonded to a terminal benzene ring in a structure having a plurality of benzene rings such as fluorene, dibenzofuran or dibenzothiophene Due to this, it is possible to provide an oxime ester compound as a photoinitiator having excellent sensitivity in a long wavelength UV light source, excellent solubility, and can minimize outgas generation.
  • the aryl group which is a substituent used in the compound of the present invention, is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and includes a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, In addition, when there is a substituent on the aryl group may be fused with a neighboring substituent (fused) with each other to further form a ring.
  • aryl group examples include a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, phenanthryl group, Aromatic groups such as pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl and the like, and the like.
  • Hydrogen atom is deuterium atom, halogen atom, hydroxy group, nitro group, cyano group, silyl group, amino group (-NH2, -NH (R), -N (R ') (R''),R' and R "are Independently an alkyl group of C 1 -C 10 , in this case an “alkylamino group”), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group of C 1 -C 24 , C 1 -C 24 halogenated alkyl group, C 2 -C 24 alkenyl group, C 2 -C 24 alkynyl group, C 1 -C 24 heteroalkyl group, C 6 -C 24 aryl group, C 7 -C 24 May be substituted with an arylalkyl group, a C 2 -C 24 heteroaryl group, or
  • the heteroaryl group which is a substituent used in the compound of the present invention, contains 1, 2 or 3 heteroatoms selected from N, O, P, Si, S, Ge, Se, Te, and C 2 -C wherein the remaining ring atoms are carbon.
  • a ring aromatic system of 24 wherein the rings can be fused to form a ring.
  • At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the case of the aryl group.
  • alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like, and one of the alkyl groups
  • the above hydrogen atoms may be substituted with the same substituents as in the case of the aryl group.
  • the above hydrogen atoms can be substituted with the same substituents as in the case of the aryl group.
  • silyl group which is a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl And dimethylfuryl silyl and the like, and at least one hydrogen atom in the silyl group may be substituted with the same substituent as in the case of the aryl group.
  • the substituents R 3 and R 4 may be bonded to each other to form a monocyclic or polycyclic ring of alicyclic or aromatic', and as an example, the substituents R 3 and R 4 are alkyl groups.
  • an alicyclic monocyclic ring may be formed, wherein s is preferably an integer of 0 to 5, and the carbon ring including s may further form an aliphatic or aromatic ring. It may include.
  • the substituents R 3 and R 4 when the substituents R 3 and R 4 is an aryl group, as shown in [Formula A-3], the substituents R 3 and R 4 may be bonded to each other to form an alicyclic or aromatic ring, wherein p is 0 to It is preferably an integer of 2, and the carbon ring containing p may include additional aliphatic or aromatic rings.
  • R 1 to R 4 , R ′ are as defined above, and m is 0 or 1.
  • the oxime ester compound represented by [Formula A-1] has a functional group including an oxime ester group bonded to one benzene ring of a fluorene group including R 3 and R 4, wherein the functional group is substituted with a substituent R 1 and One of the carbon atoms in the other benzene ring having an oxime ester group containing R 2 and optionally having a carbonyl group in the benzene ring of the fluorene group, and not having an oxime ester group in the fluorene group bonded thereto; It is a technical feature to have a structure in which the R'-S substituent is bonded.
  • R 1 , R 2 and R ′ are as defined above and m is 0 or 1.
  • the oxime ester compound represented by [Formula A-2] has a functional group including an oxime ester group bonded to one benzene ring of the dibenzothiophene group, and the functional group includes substituents R 1 and R 2 . It has an oxime ester group, and also has a structure containing a carbonyl group selectively in the benzene ring of the dibenzothiophene group, and one carbon atom in the other benzene ring to which the oxime ester group in the dibenzothiophene group is not bonded. It is a technical feature to have a structure in which the R'-S substituent is bonded.
  • R 1 , R 2 and R ′ are as defined above and m is 0 or 1.
  • the oxime ester compound represented by the above [Formula A-3] has a functional group including an oxime ester group bonded to one benzene ring of a dibenzofuran group, wherein the functional group includes an oxime ester containing substituents R 1 and R 2 A group having a group and optionally comprising a carbonyl group in the benzene ring of the dibenzofuran group, and also having one R'-S substituent at a carbon atom in the other benzene ring to which the oxime ester group in the dibenzofuran group is not bonded. It is characterized by having a combined structure.
  • R ' which corresponds to the sulfide substituent in [Formula A], which is a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 3 -C 20 cyclo It may be a substituent selected from an alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 7 -C 24 arylalkyl group.
  • R ' which corresponds to the sulfide substituent in [Formula A], it may be a substituent represented by (R 8 ) p -Ar-.
  • substituent R 8 is a substituted or unsubstituted C 1 -C 24 alkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group, a substituted or unsubstituted C 6 -C 24 aryl group, substituted or unsubstituted hwandoen of C 7 -C 24 arylalkyl group of substituted or unsubstituted C 1 -C 24 halogenated alkyl group, a substituted or unsubstituted C 1 -C 24 alkoxy group, a substituted or unsubstituted C 1 -C 24 of Alkylsilyl group, substituted or unsubstituted C 6 -C 24 arylsilyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl group, substituted or unsubstituted C 6 -C 20 arylthioyl group , A substituted or
  • the substituent R 'represented by (R 8 ) p -Ar- includes a substituted or unsubstituted C 6 -C 24 aromatic ring represented by -Ar-, and the substituent R 8 is 0 in the aromatic ring. To 3 may be substituted.
  • Ar corresponds to a substituted or unsubstituted C 6 -C 24 aryl group, and when substituted one, substituted or unsubstituted C 6 -C 24 aryl.
  • two substituents, if substituted, represent an aromatic ring in which three radicals in a substituted or unsubstituted C 6 -C 24 aromatic ring are linked to a sulfur atom or to R 8 .
  • the oxime ester compound having a substituent R 'represented by (R 8 ) p -Ar- may have an aromatic ring on one benzene ring of a fluorene group, dibenzofuran group or dibenzothiophene group depending on the type of X. Is directly bonded, the plate-like structure having a plurality of rings can be extended to provide excellent solubility characteristics, and due to this structural characteristics can further minimize the end group structure for imparting solubility to minimize outgas generation Can be.
  • R 'in [Formula A] may be a substituent represented by the following [Formula A-1].
  • the substituents R 11 to R 15 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 1 -C 24 halogenated alkyl group, substituted or unsubstituted C 6 -C 30 aryl group, substituted or unsubstituted C having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms 3 -C 24 heteroaryl group, substituted or unsubstituted C 1 -C 20 alkoxy group, substituted or unsubstituted C 7 -C 20 arylalkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group , Substituted or unsubstituted C 1 -C 24 alkylsilyl group, substituted or unsubstituted C 6 -C
  • a specific compound of the oxime ester compound represented by the [Formula A] in the present invention may be a compound represented by any one of the compounds 1 to 330 shown in Table 1 below, but is not limited thereto.
  • the present invention provides a photoresist composition
  • a photoresist composition comprising an oxime ester compound represented by the above [Formula A].
  • the oxime ester compound may be used as a photoinitiator material for photoresist that is included in a photoresist composition to provide radicals by light such as UV and the like, and the photoresist composition may be a column spacer, a flexible insulating film, an overcoat, a black matrix, or a color.
  • a photoresist composition may be a column spacer, a flexible insulating film, an overcoat, a black matrix, or a color.
  • the photoresist composition containing the oxime ester compound has excellent compatibility with a solvent or an acrylic monomer when used as a photoresist composition for a display or an electronic material, has excellent sensitivity to a UV light source, and efficiently uses UV. It is absorbed by, so it has high sensitivity and high transparency, so it can improve yield and performance when using.
  • the photoresist composition may be a water-based development by adding a polymerizable compound or solvent having an ethylenically unsaturated bond with the acrylic polymer, and may further include a photopolymerizable compound, an acrylic polymer or a solvent in the oxime ester compound,
  • the present invention is not limited thereto, and may further include materials used in other known photoresist compositions.
  • the photoresist composition of the present invention may include 0.1 to 20 parts by weight of the oxime ester compound and 80 to 99.9 parts by weight of the photopolymerizable compound with respect to 100 parts by weight of the photoresist composition.
  • the content of the photopolymerizable compound may include 80 to 99.9 parts by weight based on 100 parts by weight of the photoresist composition when used in only two components together with the oxime ester compound. That is, the content of the photopolymerizable compound may include 80 to 99.9 parts by weight based on 100 parts by weight of the photoresist composition when used in only two components together with the oxime ester compound.
  • the photoresist composition may further comprise an acrylic polymer or a solvent, at this time, based on 100 parts by weight of the photoresist composition, 0.1 to 20 parts by weight of the oxime ester compound, 1 to 60 parts by weight of the photopolymerizable compound, acrylic 0 to 40 parts by weight of the polymer and 10 to 90 parts by weight of the solvent.
  • the photoresist composition may further include a red, green, blue or black pigment, in this case with respect to 100 parts by weight of the photoresist composition, 0.1 to 20 parts by weight of the oxime ester compound, 1 to 60 of the photopolymerizable compound It may include parts by weight, 0 to 40 parts by weight of acrylic polymer, 1 to 50 parts by weight of red, green, blue or black pigment and 10 to 90 parts by weight of solvent.
  • a red, green, blue or black pigment in this case with respect to 100 parts by weight of the photoresist composition, 0.1 to 20 parts by weight of the oxime ester compound, 1 to 60 of the photopolymerizable compound It may include parts by weight, 0 to 40 parts by weight of acrylic polymer, 1 to 50 parts by weight of red, green, blue or black pigment and 10 to 90 parts by weight of solvent.
  • the photopolymerizable compound is a compound including one or two or more acrylic groups, methacryl groups or vinyl groups.
  • the photoinitiator according to the present invention refers to a compound in which radicals are generated by UV and crosslinked by the generated radicals.
  • the photopolymerizable compound include alkyl acrylates such as hexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetradecyl (meth) acrylate and hexadecyl (meth) acrylate; Alkyl methacrylate, ethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, decanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Ta-erythritol penta (meth) acryl
  • the photoresist composition according to the present invention may selectively use an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain in order to provide thin film properties such as pattern characteristics control and heat resistance.
  • the acrylic polymer is a copolymer of monomers including the monomers described below.
  • the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate and hexadecyl (meth) acrylate, isobonyl (meth ) Acrylate, dandanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, Acrylic acid, methacrylic acid, styrene, ace
  • the content of the acrylic polymer preferably includes 0 to 40 parts by weight based on 100 parts by weight of the photoresist composition when it contains a solvent.
  • the content of the acrylic polymer is mixed by 40 parts by weight or more, the viscosity of the solution is too high, there is a problem that the coating is difficult.
  • the photoresist composition of the present invention may be used by further adding a photoinitiator known as needed.
  • a photoinitiator known as needed.
  • ketones, ketoacetals, thioxanthones, phosphine oxides, anthraquinones, trichloromethyl triazines, oxime esters, and the like can be used.
  • photoinitiators include phenyl Biphenyl ketone, thioxanthone, isopropyl thioxanthone, diethyl thioxanthone, benzophenone, 1-benzyl-1-dimethylamino-1- (4-morpholino-benzoyl) propane, 1-hydroxy- 1-benzoylcyclohexane, 2-morpholinyl-2- (4-methylmercapto) benzoylpropane, ethylanthraquinone, 4-benzoyl-4-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2- Benzoylpropane, 2-hydroxy-2- (4-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, diphenyl-2,4,6-trimethylbenzoylphosphine oxide, Methyl benzoyl formate
  • the photoinitiator may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photoresist composition in order to adjust exposure sensitivity and pattern characteristics.
  • the photoinitiator may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photoresist composition in order to adjust exposure sensitivity and pattern characteristics.
  • the solvent is not only selectively used to dissolve the photoresist composition, but also used to obtain excellent coatability and a transparent thin film, and it is preferable to use an organic solvent as such a solvent.
  • organic solvent preferably ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, propylene glycol Methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexa Paddy, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), ⁇ -butyrolactone, diethyl ether, ethylene glycol dimethyl ether, digle Lime (DMF
  • the photoresist composition according to the present invention further comprises at least one colorant pigment selected from the group consisting of red, green, blue and black, if necessary, a photoresist composition for a color matrix or a photoresist composition for a black matrix It can be prepared as.
  • the content of the color colorant pigment to be added may be appropriately selected depending on the conditions of use of the photoresist, for example, 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the photoresist composition. have.
  • the content of the colorant pigment satisfies this range, the color purity and luminance characteristics of the color filter obtained are very excellent, and when the content of the pigment is added 50 parts by weight or more, there is a problem that the crystallization or the pattern characteristics are degraded when the pattern is formed. have.
  • the black pigment may be used a carbon black dispersion commonly used, but is not limited thereto.
  • the photoresist composition according to the present invention is a color filter, an organic light emitting element (OLED), an illumination device, a TFT-LCD, a metal sensor, a solar cell, an integrated circuit, an organic field-effect transistor (O-FET) and an organic thin film transistor It can be used in any one device selected from (O-TFT).
  • the oil obtained was solidified using 10 ml of ethyl acetate and 100 ml of methanol to obtain the target compound 1- (9,9). 9.0 g (92%) of -dimethyl-2- (phenylthio) -fluorene-7-yl) propan-1-one were obtained.
  • acryl copolymer 1 prepared in Synthesis Example 18 acryl copolymer 1 prepared in Synthesis Example 18 , PGMEA (to 100 parts by weight), a photopolymerizable compound and a photoinitiator were sequentially added according to the components and contents shown in Table 2 below at room temperature. Stirring for 12 hours to prepare a photoresist composition.
  • composition of the photoresist prepared from the above examples is shown in Table 2 below.
  • a photoresist was prepared in the same manner as in Example 1, except that the photoinitiator used 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione in place of compound 1. It was.
  • a photoresist was prepared in the same manner as in Example 2, except that the photoinitiator used 1- (o-benzoyloxime)-(dibenzo [b, d] furan-2-yl) pentanone instead of compound 15.
  • a photoresist was prepared in the same manner as in Example 3, except that the photoinitiator used 1- (o-acetyloxime)-(dibenzo [b, d] furan-2-yl) pentanone instead of compound 17.
  • the photoresist was spin-coated on a glass substrate, heated at 100 ° C. for 2 minutes in a hot plate, exposed using a step mask, and developed in a 0.04% KOH aqueous solution. Sensitivity was evaluated for the exposure amount in which the step mask pattern maintains 90% of the initial thickness.
  • the photoresist composition was applied onto the substrate using a spin coater, heated at 100 ° C. for 2 minutes, exposed to 500 mJ at 365 nm, and developed in a 0.04% KOH aqueous solution. Hard-bake was performed at 250 degreeC for 30 minutes, and the thickness ratio (%) before and after hard baking of the photoresist film was measured.
  • the photoresist composition was applied onto a substrate using a spin coater, then prebaked at 100 ° C. for 2 minutes, exposed to 500 mJ at 365 nm, and developed in a 0.04% KOH aqueous solution. After performing a hard bake at 250 ° C. for 30 minutes, the transmittance was measured at 400 nm using a UV-vis spectrophotometer.
  • Each 50mg of the prepared compound and the compound used in the comparative example were collected by heating at 230 ° C. for 30 minutes using a headspace device, and then measured by integrating the total amount of generated gas using a GC-Mass device. .
  • Example 1 65 94 98 72
  • Example 2 70 95 97 63
  • Example 3 71
  • Example 4 73
  • 94 94 63 Example 5
  • Example 6 65
  • Example 7 68
  • 96 96 55 Example 8
  • Example 9 72
  • Example 11 60 93 94 70
  • Example 12 80 91 96 81 Example 13 45 93 96 68
  • Example 14 50
  • Example 15 55
  • Example 16 83 89 96 78
  • Example 17 82 91 95 77
  • Example 18 50
  • Example 19 45 94 96 74
  • Example 20 95 97 79 Comparative Example 1 160 88 91 182 Comparative
  • the photoresist composition of the present invention has excellent physical properties such as sensitivity, residual film ratio, transmittance, and the like compared to the conventional photoresist composition, and can significantly reduce the amount of outgas generated during the process. There is an advantage.
  • This result can minimize the out-gas generated from the photoinitiator in the exposure and hard bake process during the TFT-LCD manufacturing process has the advantage of reducing the contamination and improved productivity by shortening the exposure time.

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Abstract

La présente invention concerne un composé aromatique substitué par un groupe ester d'oxime, son procédé de préparation, et une composition de résine photosensible le comprenant et elle est utile pour obtenir une composition photosensible qui absorbe efficacement les UV et présente une sensibilité élevée.
PCT/KR2019/005284 2018-05-11 2019-05-02 Nouveau composé d'ester d'oxime et composition de résine photosensible le comprenant WO2019216600A1 (fr)

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