KR100781873B1 - Photoactive oxime ester based compounds and photosensitive composition comprising the same - Google Patents

Abstract

The present invention provides a photoactive oxime ester compound and a photosensitive composition comprising the same.

Photoactive oxime ester compound, photosensitive composition

Description

Photoactive oxime ester compound and the photosensitive composition containing the same {PHOTOACTIVE OXIME ESTER BASED COMPOUNDS AND PHOTOSENSITIVE COMPOSITION COMPRISING THE SAME}

The present invention relates to a photoactive compound containing an oxime ester group, and more particularly, it can efficiently absorb a UV light source without the color of the compound, and in itself has a high photoinitiation efficiency, but can be used with a triazine photoinitiator. The present invention relates to a photosensitive composition comprising an oxime ester compound that causes synergy in a photopolymerization initiator.

The photosensitive composition consists of a polymerizable compound having an ethylenically unsaturated bond and a photopolymerization initiator. Since the photosensitive composition can be irradiated with light to polymerize and harden, the photocurable ink, the photosensitive printing plate, various photoresists, pigment dispersion type photosensitive material for manufacturing color filters for LCD, photosensitive material for forming a resin black matrix, transparent photosensitive material, and the like. It is used. As photopolymerization initiators used in such photosensitive compositions, various kinds of acetophenone derivatives, benzophenone derivatives, biimidazole derivatives, acylphosphine oxide derivatives, triazine derivatives and oxime derivatives are known. It is not noticeable, has high permeability, high efficiency of radical generation by UV irradiation, and it is not sensitive to oxygen.

Japanese Patent Laid-Open No. 61-118423, Japanese Patent Laid-Open No. Hei 1-68750, and Japanese Patent Laid-Open No. Hei 3-4226 use α-oxo oxime derivatives as photoresist photoinitiators for photoimaging and printed wiring boards. And described in Opt. Eng. 24 (1985) 808 and J. Opt. Eng. 27 (1988) 301 describes the use of α-oxooxime derivatives as photoinitiators of holography.

In particular, US Patent No. 4,590,145 discloses a photoinitiation system using a thiooxanthone and an oxime ester compound, and US Patent No. 4,255,513. A synergistic reference is made to an oxime ester photo-opening clock using p-dialkylaminobenzene, and US patents No. 5,776,996 describes photosensitive clocks using β-aminooximes, such as photosensitizing dyes and titanocene compounds. Doing. International Publication No. 00/52530 and German Publication No. 199 28 742 A1 describe photosensitive compositions using oxime ethers, oxime esters, in particular oxime sulfonate, as photoinitiators. International Publication No. 02/100903 A1 describes an oxime ester compound having a structure bonded with an alkyl acyl ketone, diaryl ketone or ketocoumarin.

In addition, the oxime ester structure may be used as an etch resist as in US Pat. No. 4,202,697, or as a photosensitive thermosetting accelerator in positive type photosensitive compositions as in US Pat. No. 6,001,517.

However, the compounds initially developed among the oxime derivative compounds have low photoinitiation efficiency and are not effective in absorbing UV light sources when the color characteristics are good. Compounds published after the late 1990s have significantly improved the photoinitiation efficiency, but have not fully satisfied the recently enhanced process time reduction. In particular, there is still a difficulty in forming a fine pattern because the pigment concentration or the coating film has a thickness of 2.5 micrometers or more is not satisfactorily satisfied, and the formed pattern has a critical dimension (CD) or mechanical requirement of the product. Can't make strength.

The present invention is to solve the above problems of the prior art, the inventors of the present invention after repeated studies when using a photoactive oxime ester compound of a specific structure, more preferably when used with a triazine compound of the negative type It was found that the sensitivity of the photosensitive material was excellent and the pattern satisfies the appropriate line width and mechanical strength.

An object of the present invention is to provide a photoactive oxime ester compound having a specific structure.

Another object of the present invention is to provide a photosensitive composition using the oxime ester compound, more preferably a photosensitive composition using the oxime ester compound and a triazine photoinitiator together.

The present invention to achieve the above object,

It provides a photoactive oxime ester compound selected from the group consisting of the following [Formula 1] to [Formula 4]:

Wherein R is selected from the group consisting of hydrogen, alkyl having 1 to 6 carbon atoms and phenyl, but in Formula 1 and Formula 2, R is not hydrogen, and when two or more are present in the same molecule, ,

R1, R2, R3, R4, R5 are each independently alkyl of 1 to 6 carbon atoms, halo alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms with one or more hetero elements inserted, substituted or unsubstituted phenyl, One is selected from the group consisting of alkyl carboxylic acids having 2 to 5 carbon atoms;

R 6 is selected from the group consisting of alkyl having 2 to 5 carbon atoms substituted with carboxylic acid, phenyl 2-carboxylic acid, and 2-carboxylic acid cyclohexa-4-enyl;

X is selected from the group consisting of alkylene, phenylene and tetrahydrophenylene having 2 to 6 carbon atoms.

In another aspect, the present invention provides a photosensitive composition comprising a photopolymerization initiator containing the photoactive oxime ester compound represented by the above [Formula 1] to [Formula 4] as an active ingredient.

Hereinafter, the present invention will be described in detail.

In the present invention, the oxime ester compound may be used as an active ingredient of a photopolymerization initiator in the preparation of colorless transparent photosensitive compositions and colored photosensitive compositions. Although the oxime ester compound alone exhibits photoactivity, but when used in combination with an appropriate triazine photoinitiator, the mechanical strength and pattern shape are compared with those used alone or in combination with the oxime ester compound. It shows synergy effect.

The photosensitive composition containing the photoinitiator of the present invention

a) a photoactive oxime ester compound represented by the above [Formula 1] to [Formula 4];

b) a polymerizable compound having an ethylenically unsaturated bond;

c) alkali-soluble resin binder; And

d) solvent

It is included as an essential ingredient.

In another aspect, the present invention includes the use of e) a second photoactive compound or a photosensitizer to the photoactive oxime ester compound, for a more excellent photoactive effect.

Non-limiting examples of the polymerizable compound having b) an ethylenically unsaturated bond in the constituents of the photosensitive composition according to the present invention include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) having 2 to 14 ethylene groups. ) Acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2-trisacryloyloxymethyl Of ethyl phthalic acid, propylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate A mixture of an acidic variant and dipentaerythritol hexa (meth) acrylate (trade name: TO Compounds obtained by esterifying a polyhydric alcohol such as -2348, TO-2349) with α, β-unsaturated carboxylic acid; Compounds obtained by adding (meth) acrylic acid to a compound containing glycidyl groups such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; Ester compound of the compound which has hydroxyl group or ethylenically unsaturated bond, such as phthalic acid diester of (beta) -hydroxyethyl (meth) acrylate and toluene diisocyanate adduct of (beta) -hydroxyethyl (meth) acrylate, and polyhydric carboxylic acid Or adducts with polyisocyanates; And (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; And 9,9'-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, and one or more selected from the group consisting of, but not limited thereto, those known in the art Can be used. In some cases, silica dispersions may be used for these compounds, for example, Nanocryl XP series (0596, 1045, 21/1364) and Nanopox XP series (0516, 0525) manufactured by Hanse Chemie.

Among the constituents of the photosensitive composition according to the present invention, the alkali-soluble resin binder of c) is a copolymer of a monomer containing an acid functional group and a monomer giving a film strength copolymerizable with the monomer, or the copolymer is an epoxy group. It may be a compound prepared through a polymer reaction with an ethylenically unsaturated compound containing.

The binder used in the present invention has an acid value of about 30 to 300 KOH mg / g, the weight average molecular weight is preferably in the range of 1,000 to 200,000, more preferably a binder in the range of 5,000 to 100,000 molecular weight.

Non-limiting examples of the monomer containing an acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2 -Carboxylic acid, mono-2-((meth) acryloyloxy) ethyl phthalate, mono-2-((meth) acryloyloxy) ethyl succinate, ω-carboxy polycaprolactone mono (meth) acrylate or these And mixtures thereof.

Non-limiting examples of monomers copolymerizable with monomers containing acid groups include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylic Rate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (meth ) Acrylate, tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) ) Acrylate, ethoxy Ethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) Acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3, 3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, methyl α-hydroxymethyl Acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, dicyclopentanyl (meth) acrylate, dicyclophene Carbonyl (meth) acrylate, dicyclopentanyl oxyethyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) unsaturated carboxylic acid esters such as acrylate; Aromatic vinyls such as styrene, α-methylstyrene, (o, m, p) -vinyl toluene, (o, m, p) -methoxy styrene, (o, m, p) -chloro styrene; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether; N-vinyl tertiary amines, such as N-vinyl pyrrolidone, N-vinyl carbazole, and N-vinyl morpholine; Unsaturated imides such as N-phenyl maleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide; Maleic anhydrides such as maleic anhydride and methyl maleic anhydride; Unsaturated glycidyl compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, or mixtures thereof.

As the ethylenically unsaturated compound containing the epoxy group, allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene-2 It is preferable to select at least 1 sort (s) from the group which consists of -methyl- 2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, and 1,2-epoxy-9-decene.

In addition, the said alkali-soluble binder can be used individually or in combination of 2 or more types.

Non-limiting examples of the d) solvent among the components of the photosensitive composition according to the present invention include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, Propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclopenta Paddy, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, and butyl acetate, dipropylene glycol monomethyl Ethers or mixtures of one or more thereof.

Non-limiting examples of the e) second photoactive compound which is a component added to the photoactive oxime ester compound for a better photoactive effect in the photosensitive composition according to the present invention are 2,4-trichloromethyl- (4'-meth). Methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine, 2,4-trichloromethyl- (piflonil) -6-triazine , 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 3- {4- [2,4-bis (trichloromethyl) -s-triazine-6- Il] phenylthio} propanoic acid, 2,4-trichloromethyl- (4'-ethylbiphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methylbiphenyl) -6-tri Triazine compounds such as azine; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5 Biimidazole compounds such as 5′-tetraphenylbiimidazole; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxy Methoxy) -phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl- (4-methylthiophenyl) -2-mol Acetope such as polyno-1-propane-1-one (Irgacure-907) and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure-369) Non-based compounds; O-acyl oxime compounds such as Irgacure OXE 01 and Irgacure OXE 02 from Ciba Geigy; Benzophenone compounds such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone; Thioxanthone-based compounds such as 2,4-diethyl thioxanthone, 2-chloro thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichlorobenzoyl) propyl phosphine oxide Phosphine oxide compounds such as these; 3,3'-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-Cl] Coumarin-based compounds such as -benzopyrano [6,7,8-ij] -quinolizine-11-one, and the like, and most preferably, a triazine-based compound is used. Commercially available triazine photoactive compounds are manufactured by Midori Chemical Co., Ltd. and are used by TAZ-100, TAZ-101, TAZ-102, TAZ-104, TAZ-106, TAZ-107, TAZ-110, TAZ-111, TAZ-113, TAZ-114, TAZ-118, TAZ-119, and TAZ-120.

The photosensitive composition of the present invention may further include one or more additives such as colorants, curing accelerators, thermal polymerization inhibitors, plasticizers, adhesion promoters, fillers, or surfactants as necessary.

As the colorant, one or more pigments, dyes or mixtures thereof may be used. Specifically, as the black pigment, a metal oxide such as carbon black, graphite, or titanium black may be used. Examples of carbon black include cysto 5HIISAF-HS, cysto KH, cysto 3HHAF-HS, cysto NH, cysto 3M, cysto 300HAF-LS, cysto 116HMMAF-HS, cysto 116MAF, cysto FMFEF-HS , Sisto SOFEF, Sisto VGPF, Cisto SVHSRF-HS and Sisto SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, # 2700, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, # 25, # CF9, # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B (Mitsubishi Chemical Corporation); PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX- 200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (Daegu Corporation); RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN- 820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, RAVEN-1170 (Colombia Carbon, Inc.) or mixtures thereof.

In addition, examples of the colorant to be colored are carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), perylene black (BASF K0084. K0086), cyanine black, linole yellow (CI21090), Linol yellow GRO (CI 21090), benzidine yellow 4T-564D, Victoria pure blue (CI42595), CI PIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 202, 214, 215, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; C.I. PIGMENT GREEN 7, 36; C.I. PIGMENT blue 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 28, 36, 60, 64; C.I. PIGMENT yellow 13, 14, 35, 53, 83, 93, 95, 110, 120, 138, 139, 150, 151, 154, 175, 180, 181, 185, 194, 213; C.I. PIGMENT VIOLET 15, 19, 23, 29, 32, 37, etc. In addition, a white pigment, a fluorescent pigment, etc. can also be used.

Examples of curing accelerators include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto -4,6-dimethylaminopyridine, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol Tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethyloctaethane One or more kinds selected from the group consisting of tris (3-mercaptopropionate) may be used, but are not limited thereto, and those known in the art may be used.

Thermal polymerization inhibitors include p-anisole, hydroquinone, pyrocatechol, t-butyl catechol, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine aluminum One or more selected from the group consisting of salts and phenothiazines may be used, but is not limited thereto, and those known in the art may be used.

Other plasticizers, adhesion promoters, fillers, surfactants and the like can also be used for all compounds that can be included in conventional photosensitive compositions.

The photosensitive composition of the present invention is used in a roll coater, curtain coater, spin coater, spin die coater, slot die coater, various printing, deposition, and the like, on a support such as a metal, paper, and glass plastic substrate. Can be applied to Moreover, after apply | coating on support bodies, such as a film, it is also possible to transfer on another support body, or to apply | coating to a 1st support body, and to transfer to a blanket etc., and also to a 2nd support body again, The application method is not specifically limited.

Of the components of the photosensitive composition, based on 100 parts by weight of the photosensitive composition a) 0.1 to 5 parts by weight of the photoactive oxime ester compound of the present invention, b) 0.5 to 30 parts by weight of the polymerizable compound having an ethylenically unsaturated bond, c) 1 to 20 parts by weight of the alkali-soluble resin binder, d) a solvent Is contained in an amount of 10 to 95 parts by weight, and e) 0.1 to 5 parts by weight when the second photoactive compound is further contained.

In addition, when adding other ingredients that can be added, the coloring agent may be added in an amount of 0.01 to 10 parts by weight, each of at least one selected from 0.5 to 20 parts by weight, a curing accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, a filler, and a surfactant. Can be.

Light sources for curing the photosensitive composition of the present invention include, for example, mercury vapor arc (arc), carbon arc, Xe arc and the like that emit light of 250 to 450 nm wavelength.

The photosensitive composition comprising the compound of the present invention is a photocurable paint, a photocurable ink, a photocurable adhesive, a printing plate, a photosensitive material for a printed wiring board, a pigment dispersion photosensitive material for manufacturing a TFT LCD color filter, a black matrix of a TFT LCD or an organic light emitting diode. It can be used for forming photosensitive material, photosensitive material for overcoat layer formation, column spacer photosensitive material, other transparent photosensitive material, and PDP production, and the use thereof is not limited.

The present invention will be described in more detail with reference to the following examples. However, an Example is for illustrating this invention and is not limited only to these.

Synthesis Example  1: compound of formula A [1,2- Vis (4- Acetylphenyl )-4- Formylbenzene  Tris (O-acetyl Oxime )]

a) Synthesis of 1,3-bis (4-acetylphenyl) -5-formylbenzene

13.8 g of 3,4-dihydroxybenzaldehyde (0.1 mol), 33 g of 4-fluoroacetophenone (0.24 mol) and 42 g of potassium carbonate were dissolved in 200 mL of DMF, followed by 20 at 140 ° C. The reaction was carried out for a time. After checking the progress of the reaction by TLC, the reaction solution was poured into 1 L of methylene chloride, and as a result, salt and reaction residues were formed and filtered. The filtrate was washed thoroughly with brine and water was removed with anhydrous magnesium sulfate.

Remove volatile components under reduced pressure and purify 1,3-bis (4-acetylphenyl) -5-formylbenzene compound by column chromatography using ethyl acetate / hexane cosolvent (1 / 2.5, V / V) as eluent It was. 1,3-bis (4-acetylphenyl) -5-formylbenzene was obtained in 25.9 g, 69% yield.

b) Synthesis of 1,3-bis (4-acetylphenyl) -5-formylbenzene trioxime

7.5 g of 1,3-bis (4-acetylphenyl) -5-formylbenzene (0.02 mol) was dissolved in 50 mL of cot solvent of 50 mL of EtOH and 50 mL of dioxane and placed in a 250 mL 2-neck round bottom flask. 4.9 g of hydroxylamine hydrogen chloride was dissolved in 10 g of water and poured into the reaction flask at room temperature at a time. A 20% aqueous solution of 8.4 g of NaOH in 33.6 g of water was slowly added to the reaction solution through a dropping funnel at room temperature. After the reaction occurred with exotherm at room temperature and reacted at room temperature for 2 hours, the reaction mass was heated to 50 ° C. for 10 minutes to further react and cooled to room temperature. The reaction solution was poured into 1 L of distilled water and neutralized with acetic acid. The precipitate produced at this time was washed with distilled water several times, washed with hexane and dried to obtain a pure compound 1,3-bis (4-acetylphenyl) -5-formylbenzene trioxime. 1,3-bis (4-acetylphenyl) -5-formylbenzene trioxime was obtained in 6.5 g, 78% yield.

c) Synthesis of 1,3-bis (4-acetylphenyl) -5-formylbenzene tri (O-acetyl oxime)

2.9 g of 1,3-bis (4-acetylphenyl) -5-formylbenzene trioxime (0.0070 mol) was dissolved in 50 mL THF and placed in a 100 mL 2-neck round bottom flask. 4.5 g of pyridine (0.057 mol) was added thereto, and stirring was started with a magnetic spoon. The flask was equipped with a dropping funnel and 3.7 g of diluted acetyl chloride (0.047 mol) was added to 10 mL of THF. At the beginning of the dropping, salts were formed with exotherm, and the cloudy flask was stirred for 4 hours at room temperature, and then the reaction was terminated because there was no change in TLC phase. The reaction mixture was diluted with ether, extracted with distilled water, dried over magnesium sulfate, and then separated by silica gel column chromatography using hexane / ethyl acetate = 1/2 as eluent. 1,3-bis (4-acetylphenyl) -5-formylbenzene tri (O-acetyl oxime) was obtained in 1.3 g, 35% yield.

¹ H NMR (500 MHz, CDCl ₃ , ppm) 8.27 (1H, s, -N = CCH ₃ ), 7.84 (4H, m, ArH), 7.03 (6H, m, ArH), 6.76 (1H, s, ArH ), 2.34 (6H, s, -N = CCH ₃ ), 2.24 (9H, bs, O = CCH ₃ )

UV (CH ₃ CN) λ _max = 263 nm

Synthesis Example  2: compound of formula B (2,4- Bis (4'-acetylphenyl) benzophenone  Preparation of Bis (O-acetoxim)

a) Synthesis of 2,4-bis (4'-acetylphenyl) benzophenone

5.0 g (23.3 mmol) of 2,4-dihydroxybenzophenone, 6.4 g of 4-fluoroacetophenone (46.6 mmol) and 12.8 g (93.2 mmol) of potassium carbonate were dissolved in 50 mL of DMF and then 125 ^o The reaction was carried out at C for 40 hours. After checking the progress of the reaction by TLC, the mixture was extracted three times with ethyl acetate (300 mL) in 200 mL of distilled water, and the organic layer was separated and water was removed with anhydrous magnesium sulfate. Under reduced pressure, the volatile components were removed and the synthesized compound was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/1 as eluent. 2,4-bis (4'-acetylphenyl) benzophenone was obtained in 3.4 g, 32% yield.

b) Synthesis of 2,4-bis (4'-acetylphenyl) benzophenone dioxime

Dissolve 5.5 g (12.2 mmol) of 2,4-bis (4'-acetylphenyl) benzophenone prepared in step a) in 90 mL of ethanol, and 2.6 g of hydroxylamine hydrogen chloride with 1.8 g (26.8 mmol). (31.7 mmol) of sodium acetate was placed in a flask dissolved in 30 g of water. The reaction was heated to 80 ° C. and refluxed for 1 hour to observe the degree of reaction by TLC. After completion of the reaction, water (500 mL) was added to the reaction mixture to generate a white solid, which was filtered, washed with water and dried to give 5.2 g of 2,4-bis (4'-acetylphenyl) benzophenone dioxime. , 89% yield.

c) Synthesis of Compound of Formula B (2,4-bis (4'-acetylphenyl) benzophenone bis (O-acetoxime))

2.4 g (10.8 mmol) of 2,4-bis (4'-acetylphenyl) benzophenone dioxime and 1.9 g (23.8 mmol) of pyridine prepared in step b) were dissolved in a flask of 50 mL of dichloromethane. g (23.8 mmol) of acetic anhydride was added thereto and stirred at room temperature overnight. After this time the solvent was removed in vacuo and the product was purified by column chromatography (chloroform). As a result, the compound of formula B (2,4-bis (4'-acetylphenyl) benzophenone bis (O-acetoxim)) was obtained in 3.7 g, 60% yield and the structure was confirmed by NMR.

¹ H NMR (500 MHz, CDCl ₃ , ppm) 7.78 (4H, d, ArH), 7.63 (2H, d, ArH), 7.58 (1H, d, ArH), 7.53 (1H, d, ArH), 7.42 ( 2H, dd, ArH), 7.10 (2H, d, ArH), 6.88 (1H, dd, ArH), 6.80 (2H, d, ArH), 6.66 (1H, d, ArH), 2.38 (3H, s, N = CCH ₃ ), 2.31 (3H, s, N = CCH ₃ ), 2.26 (3H, s, O = CCH ₃ ), 2.24 (3H, s, O = CCH ₃ ).

UV (CH ₃ CN) λ _max = 264 nm

Synthesis Example  3: compound of the formula C [2- Formyl Fluorene Oxime  O- (succinic acid ester)]

a) Synthesis of 2-formyl fluorene oxime

15.0 g (77 mmol) of fluorene-2-carboxaldehyde was dissolved in 140 mL of ethanol, and 5.9 g (84 mmol) of hydroxylamine hydrogen chloride and 8.3 g (100 mmol) of sodium acetate were dissolved in 50 g of water. Put it in the dissolved flask. The reaction was heated to 80 ° C. and refluxed for 1 hour to observe the degree of reaction by TLC. After completion of the reaction, water (300 mL) was added to the reaction mixture to generate a white solid, which was filtered, washed with water and dried to give 2-5.8 fluorine oxime in 15.8 g, 97% yield.

b) Synthesis of Compound of Formula C (2-formyl fluorene O-acetoxim)

2.3 g (10.9 mmol) of 2-formyl fluorene oxime prepared in step a), 1.0 g (10.9 mmol) of succinic anhydride, and 1.3 g (13 mmol) of triethylamine were dissolved in 30 mL of dichloromethane overnight at room temperature. Stirred. The reaction mixture was diluted with ethyl acetate and then the organic layer was washed twice with 1 N hydrochloric acid and dried over sodium sulfate. After this time the solvent was removed in vacuo and the product was purified by passing through a short column. As a result, 1.0 g, 30% yield of the compound of formula 2B [2-formyl fluorene oxime O- (succinic acid ester)] was obtained, and the structure was confirmed by NMR.

¹ H NMR (500 MHz, Acetone-d ₆ , ppm, mixed with 2 isomers) 10.80 (2H, bs, 2CO ₂ H), 9.32 (1H, s, N = CH), 8.61 (1H, s , N = CH), 8.19 (1H, d, ArH), 8.02 (1H, d, ArH), 8.00 (1H, d, ArH), 7.96 (1H, d, ArH), 7.83 (2H, m, ArH) , 7.76 (1H, d, ArH), 7.66 (2H, m, ArH), 7.45 (5H, m, ArH), 4.01 (4H, ss, ArCH ₂ Ar), 2.90 (2H, s, O = CCH ₂ ) , 2.85 (2H, s, CH ₂ C = O), 2.78 (4H, ss, O = CCH ₂ CH ₂ C = O)

UV (CH ₃ CN) λ _max = 308 nm

Synthesis Example  4: compound of formula D [ Vis  (2- Formyl Fluorene Oxime ) O-succinate]

In a solution of 3.0 g (14 mmol) of 2-formyl fluorene oxime and pyridine (40 mL) prepared in step a) of Synthesis Example 3, succinyl chloride (1.2 g, 7.7 mmol) was dropped at room temperature. After stirring for 3 hours at room temperature, the reaction solution was poured into 300 mL of water, the resulting white precipitate was filtered off and recrystallized from ethanol. As a result, 2.2 g, 42% yield of the compound of formula D [Bis (2-formyl fluorene oxime) O-succinate] was obtained, and the structure was confirmed by NMR.

¹ H NMR (500 MHz, Acetone-d ₆ , ppm) 8.60 (2H, s, -N = CH), 8.02 (6H, m, ArH), 7.84 (2H, d, ArH), 7.69 (2H, d, ArH), 7.41 (4H, m, ArH), 4.01 (2H, s, ArCH ₂ Ar), 2.85 (4H, s, O ₂ CCH ₂ )

UV (CH ₃ CN) λ _max = 312 nm

(Structure of Compound of Synthesis Example) compound rescue A

B

C

D

Example  One

10 parts by weight of an alkali-soluble resin binder BzMA / MAA (molar ratio: 70/30, Mw: 15,000), 10 parts by weight of dipentaerythritol hexaacrylate as a polymerizable compound, and a compound of Formula A prepared in Synthesis Example 1 using a photopolymerization initiator By weight, 0.5 parts by weight of TAZ-110 (Midori Chemical), and 77.5 parts by weight of PGMEA, an organic solvent, were mixed using a stirrer for 3 hours. The solution of the photosensitive composition obtained by filtering the solution with a 5 micron filter was then spin coated onto glass and subjected to electrothermal treatment at about 100 ° C. for 2 minutes to form a uniform film having a thickness of about 2.8 μm.

Using a square or circle photomask, the film was maintained at 200 μm under a high pressure mercury lamp, and exposed to an energy of 150 mJ / cm 2, and then the pattern was exposed to a pH 11.3 to 11.7 aqueous KOH aqueous solution. Developed and washed with deionized water. After the heat treatment was performed for about 40 minutes at 200 ° C., the pattern state was observed with a pattern profiler to form columnar column spacer patterns.

Example  2

In the same manner as in Example 1 except for using the compound of Formula B instead of the compound of Formula A in Example 1.

Comparative example  One

Instead of the compound of Formula A and TAZ-110 of Example 1, 2.5 parts by weight of Irgacure-369 was used in the same manner as in Example 1.

Example  3

40 g of a 20% dispersion of carbon black (8.0 g of carbon black), 4 parts by weight of an alkali-soluble resin binder BzMA / MAA (molar ratio: 80/20, Mw: 24,000), 3 weights of dipentaerythritol hexaacrylate as a polymerizable compound 2 parts by weight of the compound of Formula C prepared in Synthesis Example 3, 0.5 parts by weight of TAZ-110 (Midori Chemical), and 50.5 parts by weight of PGMEA, which is an organic solvent, were mixed with a stirrer for 3 hours. The solution of the photosensitive composition obtained by filtering the solution with a 5 micron filter was then spin coated onto glass and subjected to electrothermal treatment at about 100 ° C. for 2 minutes to form a uniform film having a thickness of about 1.1 μm.

The film was exposed under a high pressure mercury lamp using a line and space type photomask, and then the pattern was developed with an aqueous KOH alkali solution of pH 11.3-11.7 and washed with deionized water. After the heat treatment was performed for about 40 minutes at 200 ℃, the state of the pattern was observed by an optical microscope and a pattern profiler.

Example  4

Except for using the compound of formula D prepared in Synthesis Example 4 and was the same as in Example 3.

Comparative example  2

Instead of the compound of Formula C and TAZ-110 of Example 3, 2.5 parts by weight of Irgacure-369 was used in the same manner as in Example 3.

Application Result 1 ( Top and Bottom Sizes of the Column Spacer Pattern and Line Width vs. Mask)

(The result of applying the photosensitive composition according to the present invention to the column spacer) Composition 95% _CD / B_CD ^* mask contrast bottom CD ^** Strain (μm) *** Example 1 0.58 27 0.23 Example 2 0.57 27 0.23 Comparative Example 1 0.52 25 0.29

* Diameter at 95% of the height of the spacer / diameter of the bottom surface (0%) of the spacer

** Bottom diameter when using 12 micron circle mask, Target: mask diameter x 2

*** Maximum Load 80mN, Acceleration = 8s, Loading Creep = 10s, Deceleration = 8s, Unloading Creep = 10s

Table 2 shows that 95% _CD / B_CD of Example 1 and Example 2 according to the present invention are larger than Comparative Example 1, and thus, the shape of the pattern is close to a cylindrical shape, and the line width is suitable for the process. It can be seen that the deformation is small. However, in the case of Comparative Example 1, the shape of the pattern is disk-shaped, and the deformation is large, so that it is weak to external force after the LCD cell bonding, and thus, the functionality as a column spacer is weak.

Application result 2

(Result of applying the photosensitive composition according to the present invention to a resin black matrix) Composition Minimum pixel size ^* Sensitivity ^** Example 3 20 60 Example 4 18 60 Comparative Example 2 28 120

* Minimum size of line and space pattern remaining after exposure for 150 mJ / cm ² and developing for 80 seconds

** Minimum exposure dose with a minimum pixel size of 25 μm or less after 60 seconds of development

Through Table 3, in the case of Example 3 and Example 4 according to the present invention as a result of applying the photosensitive composition to the resin black matrix, it was confirmed that the minimum pixel size is 18 ~ 20 ㎛, significantly lower than 28 ㎛ of Comparative Example 2 It can be confirmed that the sensitivity is also remarkably excellent.

As such, it can be seen that the photosensitive composition according to the present invention is excellent in the sensitivity and mechanical strength of the photosensitive material, and the line width is appropriate.

When using the photoactive oxime ester compound of this invention, More preferably, when it is used together with a triazine type compound, it is excellent in the sensitivity of the negative type photosensitive material, the pattern is appropriate in line width, and excellent in mechanical strength.

Claims (12)

A photoactive oxime ester compound selected from the group consisting of the following Chemical Formulas 1 to 4: [Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

Wherein R is selected from the group consisting of hydrogen, alkyl having 1 to 6 carbon atoms and phenyl, but in Formula 1 and Formula 2, R is not hydrogen, and when two or more are present in the same molecule, , R1, R2, R3, R4, R5 are each independently alkyl of 1 to 6 carbon atoms, halo alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms with one or more hetero elements inserted, substituted or unsubstituted phenyl, One is selected from the group consisting of alkyl carboxylic acids having 2 to 5 carbon atoms; R 6 is selected from the group consisting of alkyl having 2 to 5 carbon atoms substituted with carboxylic acid, phenyl 2-carboxylic acid, and 2-carboxylic acid cyclohexa-4-enyl; X is selected from the group consisting of alkylene, phenylene and tetrahydrophenylene having 2 to 6 carbon atoms. The photoactive oxime ester compound of claim 1, wherein the compound represented by Formula 1 is a compound represented by Formula A below. [Formula A]

The photoactive oxime ester compound of claim 1, wherein the compound represented by Formula 2 is a compound represented by Formula B below. [Formula B]

The photoactive oxime ester compound of claim 1, wherein the compound represented by Chemical Formula 3 is a compound represented by the following Chemical Formula C. [Formula C]

The photoactive oxime ester compound of claim 1, wherein the compound represented by Formula 4 is a compound represented by Formula D below. [Formula D]

Based on 100 parts by weight of the photosensitive composition, a) 0.1 to 5 parts by weight of the photoactive oxime ester compound according to any one of claims 1 to 5; b) 0.5 to 30 parts by weight of a polymerizable compound having an ethylenically unsaturated bond; c) 1 to 20 parts by weight of an alkali-soluble resin binder; And d) 10 to 95 parts by weight of solvent Photosensitive composition comprising a. The photosensitive composition of claim 6, further comprising 0.1 to 5 parts by weight of the second photoactive compound. The photosensitive composition as claimed in claim 7, wherein the second photoactive compound is a triazine photoinitiator. The method of claim 8, wherein the triazine-based photoinitiator is 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl)- 6-triazine, 2,4-trichloromethyl- (piflonil) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 3 -{4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid, 2,4-trichloromethyl- (4'-ethylbiphenyl) -6- Triazine, and 2,4-trichloromethyl- (4'-methylbiphenyl) -6-triazine is at least one member selected from the group consisting of. The photosensitive composition of claim 6, further comprising at least one additive selected from the group consisting of colorants, curing accelerators, thermal polymerization inhibitors, plasticizers, adhesion promoters, fillers, and surfactants. The photosensitive composition of claim 10, wherein the colorant is added in an amount of 0.5 to 20 parts by weight. The photosensitive composition according to claim 10, wherein at least one selected from the curing accelerator, the thermal polymerization inhibitor, the plasticizer, the adhesion promoter, the filler, and the surfactant is added in an amount of 0.01 to 10 parts by weight, respectively.