JP6778266B2 - An oxime ester compound having excellent heat stability, a photopolymerization initiator containing the same, and a photosensitive resin composition. - Google Patents

Description

The present application claims the benefit of priority under Korean Patent Application No. 10-2015-0134985 dated September 23, 2015, and all the contents disclosed in the literature of the Korean patent application are part of this specification. Included as a part.
The present invention relates to an oxime ester compound and a photopolymerization initiator using the same, and more specifically, a photosensitive resin composition having high brightness, excellent thermal stability, and excellent solubility in an organic solvent. The present invention relates to an oxime ester compound having a novel structure useful for production, and a photopolymerization initiator containing the same.

The photosensitive composition is obtained by adding a photopolymerization initiator to a binder resin and a polymerizable compound having an ethylenically unsaturated bond, and the photosensitive composition is polymerized by irradiating the photosensitive composition with light of 365 to 435 nm. Because it can be cured, it is used in inkjet inks or transparent or colored protective films in automobiles, mobile phones, etc., and has recently been widely used in Flat panel display (FPD) TVs, of which LCD TVs. It has been.

Manufacturing LCDs requires a variety of optical technologies and numerous electronic components, one of the most important parts of LCD manufacturing, which has red, green, blue and black pixels. It is a color filter. The color filter is manufactured by a photoetching method using a phenomenon in which the solubility is reduced by a polymerization reaction with light, and a photopolymerization initiator is applied to a hue-specific photosensitive composition used in the color filter.

High production efficiency, photospeed, sensitivity of photopolymerization with minimum exposure, and the like are important for the photosensitive resin composition, and the most important factor affecting this is the photopolymerization initiator. For example, in the case of a color filter, if the content of the coloring material is large, there is a problem that the sensitivity, developability, resolution, adhesion, etc. of the photosensitive resin composition are deteriorated, which not only reduces the productivity but also the productivity. It is known that the accuracy and reliability required for color filters cannot be obtained. That is, the color filter is required to have high sensitivity and high resolution at high density, and the photosensitive resin composition for black matrix also has high sensitivity and high resolution under the conditions of a thin film and high light-shielding property (high density). It is required to be able to exert sex.

In the case of existing regular products, there is a limit to their application due to the problem of low thermal stability, and therefore, a photoinitiator with improved thermal stability is an urgent reality.
Therefore, there is a high demand for an oxime ester compound having a new structure capable of fundamentally solving such a problem, and a negative photosensitive resin composition containing the oxime ester compound.

An object of the present invention is to solve the above-mentioned problems of the prior art and the technical problems requested from the past.

Specifically, the inventor of the present application, after repeating in-depth research and various experiments, made the oxime ester compound having a novel structure as described below more transparent and more transparent than the initiator of the prior art. It has excellent thermal stability, and when applied to a negative photosensitive resin composition, there is almost no change in brightness reduction phenomenon or resin transparency, excellent resolution, developability, adhesion, etc., and excellent thermal stability. After confirming that, the present invention was completed.

The present invention provides an oxime ester compound represented by the following chemical formula 1.
Chemical formula 1
In the above formula
R ₁ is a methyl or phenyl group
R ₂ and R ₃ are independently selected from hydrogen, methyl group, ethyl group, propyl group, and butyl group, respectively.
n is an integer of 1 to 4 and
m is an integer from 0 to 6,
However, when n is 1, m is an integer of 1 to 6.

The present invention also provides a photopolymerization initiator containing the oxime ester compound as an active ingredient.
The present invention also provides a photosensitive resin composition containing a binder resin, a compound having an ethylene-based unsaturated bond, and the photopolymerization initiator.

Since the oxime ester compound according to the present invention is excellent in storage stability, polymerization does not occur in the storage state, and the polymerizable composition can be efficiently polymerized in a short time. In addition, since it has excellent solubility in PGMEA (Propylene glycol monomethyl ether acetate), which is a solvent mainly used for color filters, it has excellent transparency and chemical resistance when applied as a photoinitiator of a photoresist composition. Excellent, when applied to column spacers, overcoats, organic insulating films, color filters, and black matrices, which are LCD manufacturing processes, there is almost no change in the brightness of the resin composition and the transparency of the resin, which causes quality problems. It is possible to produce a photopolymerization initiator and a photosensitive composition that are minimized and have excellent thermal stability.

The present invention provides an oxime ester compound represented by the following chemical formula 1.
Chemical formula 1
In the above formula
R ₁ is a methyl or phenyl group
R ₂ and R ₃ are independently selected from hydrogen, methyl group, ethyl group, propyl group, and butyl group, respectively.
n is an integer of 1 to 4 and
m is an integer from 0 to 6,
However, when n is 1, m is an integer of 1 to 6.

Specifically, the oxime ester compound according to the present invention can be selected from the group consisting of the following compounds, but is not limited thereto.

Oxime used as a starting material during production of the oxime ester compounds according to the invention, the standard chemistry textbooks (for example, J.March, Advanced Organic chemistry, 4 th Edition, Wiley Interscience, 1992) or specialized monographs (e.g., It can be obtained by the various methods described in SRSandler & W.Karo.Organic functionalgroup preparations, Vol.3.Academic Press).

The present invention provides a photopolymerization initiator containing the oxime ester compound as an active ingredient.
The photopolymerization initiator according to the present invention has higher sensitivity than existing initiators, is excellent in resolution, developability, adhesion, etc., and is excellent in solubility in PGMEA, which is a solvent mainly used in the LCD manufacturing process. It is used in all industries that perform photocuring such as LCD color filters, black matrices, column solvents, organic insulating films, and overcoats.

The present invention also provides a photosensitive resin composition containing a binder resin, a compound having an ethylene-based unsaturated bond, and the photopolymerization initiator. The amount of the photopolymerization initiator added is not particularly limited, but the oxime ester compound according to the present invention is preferably used with respect to 100 parts by weight of the polymerizable compound solid content having an ethylenically unsaturated bond. It may be included in 1 to 50 parts by weight, more preferably 5 to 30 parts by weight.

The compound having an ethylene-based unsaturated bond is a compound used in a conventional photosensitive resin composition, and is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth). Acrylate, Polyethylene Glycol Di (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Trimethylol Propantri (Meta) Acrylate, Triethylene Glycol (Meta) Acrylate, Dipentaerythritol Acrylate, Gglycerol Examples thereof include various acrylic acid esters such as meta) acrylate, melamine (meth) acrylate and epoxy (meth) acrylate, and methacrylic acid esters, (meth) acrylic acid, styrene, and acrylonitrile. Further, bisphenol A type epoxy di (meth) acrylate, bisphenol fluorene type epoxy di (meth) acrylate and the like are desirable, but the present invention is not limited to these.

Such a compound having an ethylene-based unsaturated bond can be used alone or in combination of two or more. The compound can be used in a ratio of usually 5 to 60% by weight, preferably 10 to 50% by weight, based on the total solid content weight of the negative photosensitive resin composition according to the present invention. Further, based on the total weight of the photosensitive resin composition, it may be 0.001 to 50% by weight, preferably 0.1 to 7% by weight.

Further, in the negative photosensitive resin composition according to the present invention, in addition to the oxime ester compound of the present invention, another kind of photopolymerization initiator can be used in combination as a photopolymerization initiator. Synergistic effects can also be achieved by using other types of photopolymerization initiators together.

The negative photosensitive resin composition containing such a photopolymerization initiator is decomposed very efficiently and efficiently generates radicals even if an increasing / decreasing agent is not used in combination with light irradiation in a specific wavelength region. It can be used as a high-sensitivity material.

As the photopolymerization initiator that can be used together with the oxime ester compound of the present invention, conventionally known compounds can be used, and as desirable examples, benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3'-dimethyl -4-methoxybenzophenone, benzoyl benzoic acid, esterified product of benzoyl benzoic acid, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl dimethyl ketal, 2-butoxyethyl-4-methylamino benzoic acid, chlorothioxanthone, methyl thioxanthone, Ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, diisopropylthioxanthone, dimethylaminomethylbenzoic acid, dimethylaminobenzoic acid isoamyl ester, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-Hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methyl benzoyllate, 2-Methyl-1- (4-Methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2,2' -Bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra- (4-) Phenyl) bisimidazole, 2,4-bis (dichloromethyl) -6- (4-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (richloromethyl) -1,3 , 5-s-triazine, 2,4-bis (tribromomethyl) -6- (4'-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (tribromomethyl) -1,3,5-s-triazine, 2,4-bis (trichloromethyl) -6- (1,3-benzodioxolan-5-yl) -1,3,5-s-triazine, 1- (4) -Phenylsulfanylphenyl) Butane-1,2-dione-2-oxime-O-benzoic acid, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1-( 4-Methylsulfanylphenyl) Butane-1-onoki Sim-O-acetate, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etc., but only these It is not limited to.

Such photopolymerization initiators can be used alone or in admixture of two or more at any ratio as required. In the present invention, the photopolymerization initiator is usually 0.5 to 30% by weight, preferably 1 to 20% by weight, based on the total solid content of the negative photosensitive resin composition according to the present invention. it can. Further, based on the total weight of the photosensitive resin composition, it may be 0.01 to 10% by weight, preferably 0.1 to 7% by weight.

As the binder resin, a compound having an unsaturated carboxyl group and a copolymer of another monomer copolymerizable therewith can be used.

The compound having an unsaturated carboxyl group can be used without limitation as long as it is a carboxylic acid compound having an unsaturated double bond capable of polymerizing. Specifically, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; anhydrides of the dicarboxylic acids; and ω-carboxypolycaprolactone mono (meth) acrylate and the like. Mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, monomethyl maleate, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2-carboxylic acid, mono-2-((meth) acryloyl) Examples thereof include oxy) ethylphthalate, mono-2-((meth) acryloyloxy) ethylsuccinic acid or a mixture thereof, and the above-exemplified compounds having an unsaturated carboxyl group may be used alone or in combination of two or more. It can be used, but is not limited to these. Among the compounds having an unsaturated carboxyl group, acrylic acid and methacrylic acid are preferably used because they have excellent copolymerizability and solubility in a developing solution.

The other monomer copolymerizable with the monomer having a carboxyl group can be used without limitation as long as it is a monomer having a carbon-carbon unsaturated bond. Specifically, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Unsaturated carboxylate compounds such as benzyl acrylate and benzyl methacrylate; unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; vinyl carboxylates such as vinyl acetate and vinyl propionate. Hydroate compounds; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile; 3-methyl-3-acrylicoxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acrylic Oxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-acrylicoxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acrylicoxyethyloxetane, 3- Examples thereof include unsaturated oxetane carboxylate compounds such as methyl-3-methacryloxyethyl oxetane. The other monomers copolymerizable with the above-exemplified compound having an unsaturated carboxyl group can be used alone or in combination of two or more, but are not limited thereto. ..

The binder resin can be an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain.

Further, as the binder resin, a cardo-based resin generally used in the black matrix field and represented by the following chemical formula 2 can be used.
Chemical formula 2

In the chemical formula 2, Q is a tetravalent organic group, and z is an integer of 1 or more indicating a repeating unit.

The cardo-based resin is preferably bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4). -Hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane and bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane , Bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane and bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5) -Dichlorophenyl) methane and bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane and 2,2-bis (4-hydroxy-3-chlorophenyl) ) Propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether and bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxy) Phenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromo) Phenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3, It can be obtained from 5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, etc. It is not limited to these.

The weight average molecular weight (Mw) of the binder resin can be between 2,000 and 1,000,000, preferably 3,000 and 400,000. If the average molecular weight is 2,000 or less or 400,000 or more, the sensitivity and developability may deteriorate.

In the present invention, the binder resin may be contained in an amount of 5 to 60% by weight, preferably 10 to 40% by weight, based on the total solid content of the photosensitive resin composition. If the binder resin is within the content range, a pattern can be formed and the resolution and the residual film ratio are improved, but if it is out of the range, the resolution and the residual film ratio may decrease, which is desirable. Absent.

In the photosensitive resin composition according to the present invention, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, tert-butylcatechol, phenothiazine; plasticizers; adhesion promoters; fillers and the like are commonly used. Additives can be added.

Further, the photosensitive resin composition according to the present invention may further contain one or more selected from a coloring material, an inorganic compound, a dispersant and a silane-based coupling agent.

The photosensitive resin composition of the present invention may further contain a coloring material. Examples of the coloring material include pigments, dyes, natural pigments, and the like, and these coloring materials can be used alone or in combination of two or more.

Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindolin compounds; quinacridone compounds; antantron compounds; Perinone compound; perylene compound; diketopyrrolopyrrole compound; thioindigo compound; dioxazine compound; triphenylmethane compound; quinophthalone compound; naphthalenetetracarboxylic acid; metal complex compound of azo dye and cyanine dye; lake pigment; furnace ) Method, carbon black obtained by the channel method or thermal method, or carbon black such as acetylene black, ketjen black or lamp black; the carbon black prepared or coated with an epoxy resin, said carbon. Black is pre-dispersed with a resin from a solvent to adsorb 20 to 200 mg / g of resin, the carbon black is subjected to acidic or alkaline surface treatment, the average particle size is 8 nm or more, and the amount of DBP oil absorbed. Is 90 ml / 100 g or less, and the total amount of oxygen calculated by CO and CO ₂ in the volatile matter at 950 ° C. is 9 mg or more per 100 m ^{2 of} carbon black surface area; graphite, graphitized carbon black, activated carbon, Carbon fibers, carbon nanotubes, carbon microcoils, carbon nanohorns, carbon aerogels, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese-based, ferrocyanides, Organic or organic phosphates such as ultramarine, navy blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, iron tan (red iron oxide (III)), cadmium red, synthetic iron black, amber, etc. Inorganic pigments can be used. These pigments can be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, the content of the coloring material is preferably 50 to 350 parts by weight, more preferably 100 parts by weight, based on 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond. It can be up to 250 parts by weight.

If the amount of the coloring material is contained in an excessive amount or a small amount in a desired range for expressing a desired color, a negative photosensitive resin composition having an appropriate color intended by the present invention cannot be obtained. So it is not desirable.

The photosensitive resin composition according to the present invention can also contain an inorganic compound. Examples of the inorganic compound include composite metal oxide pigments, carbon black, black low-order titanium nitride, titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, Bengala, ultramarine blue, dark blue, and chromium oxide. , Antimon white, iron black, lead tan, zinc sulfide, cadmium yellow, cadmium red, zinc, manganese violet, cobalt violet, barium sulfate, metal oxides such as magnesium carbonate, metal sulfides, sulfates, metal hydroxides, Metal carbonates and the like can be mentioned, but are not limited to these. These inorganic pigments can be used alone or in combination of two or more, if necessary. In the negative photosensitive resin composition of the present invention, the content of the inorganic compound is preferably 0.1 to 1000 parts by weight, preferably 0.1 to 1000 parts by weight, based on 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond. Can be 10 to 800 parts by weight.

A dispersant that disperses a coloring material and / or an inorganic compound can be added to the photosensitive resin composition of the present invention. As the dispersant, any dispersant that is not limited as long as it can disperse and stabilize a coloring material or an inorganic compound, for example, the BYK series, which is a product of Big Chemie, is used. Can be done. In particular, a polymer dispersant made of polyester, polyether, or polyurethane having a basic functional group, an amine as a basic functional group and a functional group having a nitrogen atom, and / or a quaternary salt thereof. It is preferably used that has an amine value of 1 to 100 mgKOH / g.

Further, a silane-based coupling agent is added to the photosensitive resin composition of the present invention in order to improve the adhesion between the glass substrate and the photosensitive resin film. As the silane coupling agent containing vinylalkoxy, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane and the like can be used. Examples of the silane coupling agent containing (meth) cryloxy include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane. , 3-Acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, and the like can be used. These addition ratios can be 0.01 to 2% by weight, more preferably 0.05 to 0.5% by weight, based on the total solid content of the negative photosensitive resin composition.

Further, in the photosensitive resin composition of the present invention, a solvent is used as necessary for adjusting the viscosity, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monopropyl ether. Ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate. , Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate, benzene, toluene, xylene, mesitylene. Aromatic hydrocarbons such as, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, alcohols such as glycerin, 3-ethoxypropion Examples thereof include esters such as ethyl acid and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

As the solvent, an organic solvent having a boiling point of 100 ° C. to 200 ° C. is preferably used from the above-exemplified solvents in terms of coatability and drying property, and alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate. And esters such as methyl 3-methoxypropionate are more preferably used, especially propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like. Desirably used. The solvent can be used alone or in combination of two or more. It is desirable to select the ratio of the solvent so that the resin liquid has a viscosity to be applied to the substrate, and it is usually 10 to 95% by weight, preferably 20 to 80% by weight based on the total weight of the photosensitive resin composition. Can be included.

In addition, the photosensitive resin composition according to the present invention contains other additives such as a chain transfer agent, an increase / decrease agent, a surfactant, an antioxidant, and a stabilizer within a range that does not impair the physical properties of the resin composition. It is added in a certain amount. The amount of such additives added will be adjusted by those skilled in the art.
Color filters, black matrices, column spacers, organic insulating films, overcoats, and the like can be produced using such photosensitive resin compositions.

Specifically, the present invention can provide a color filter containing the photosensitive resin composition. The negative photosensitive resin composition used for such a color filter contains, for example, pigment blue representing blue, 15: 6 in an amount of 20 to 30% by weight, preferably 23 to 27% by weight, based on the total solid content. , For example, 25% by weight can be included to represent blue.

The present invention also provides a black matrix containing the photosensitive resin composition. The negative photosensitive resin composition used for such a black matrix contains, for example, 10 to 15% by weight, preferably 11 to 13% by weight, based on the total solid content of carbon black representing black, for example, about. It can represent black by including 12.4% by weight.

Hereinafter, the methods for these will be specifically described as follows.

In the method for producing a color filter and a black matrix of the present invention, the dye-containing negative curable resin composition of the present invention is applied onto a support by a coating method such as rotary coating, flexible coating, or roll coating, and is radiation-sensitive. A negative type coloring pattern is formed by forming a resin composition layer, exposing the layer through a predetermined mask pattern, and developing with a developing solution (image forming step). In addition, if necessary, a curing step of curing the formed coloring pattern by heating and / or exposure may be included.

In the production of the color filter of the present invention, a color filter having a desired hue can be produced by repeating the image forming step (and the curing step if necessary) for a desired number of hues. At this time, as the light or radiation used, ultraviolet rays such as g-ray, h-ray, and i-ray can be preferably used.

Examples of the support include soda glass, Pyrex (R) glass, and quartz glass used for liquid crystal display elements, those to which a transparent conductive film is attached, and photoelectric conversion element substrates used for image pickup elements and the like. For example, a silicon substrate and the like, a complementary metal oxide film semiconductor (CMOS) and the like can be mentioned. These supports may be formed with black stripes that isolate each pixel.

In addition, a primer layer can be formed on these supports, if necessary, for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the surface of the support.

As the developing solution, any uncured portion of the dye-containing negative curable resin composition of the present invention can be used, while the irradiation portion has a composition that does not dissolve. Specifically, as the developer, a combination of various organic solvents and an alkaline aqueous solution can be used. Examples of the organic solvent include the above-mentioned organic solvent used for preparing the dye-containing negative curable resin composition of the present invention. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like. Alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution made by dissolving in this way is used. Further, when a developer composed of such an alkaline aqueous solution is used, it can generally be washed with water after development.

One or more such color filters, black matrices, or column spacers are included in a liquid crystal display device or a solid-state image sensor and are usefully used.
The liquid crystal display device can be manufactured in the order of, for example, a backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, a color filter of the present invention, a polarizing film, and the like.

Further, the solid-state image sensor can be manufactured, for example, by forming the color filter layer of the present invention on a silicon wafer on which a transmission electrode and a photodiode are formed, and subsequently laminating microlenses.
Hereinafter, the contents of the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited thereto.

[Example 1] 1- (9,9-Dipropyl-9H-fluorene-2-yl) -1,2-octanedione-2-oxime-O-acetate compound 1 synthetic synthesis 1-1) 9,9- Synthesis of dipropyl-9H-fluorene (1)

It was dissolved in 10.0 g of fluorene and 100 mL of tetrahydrofuran, 16.2 g of 1-bromopropane was added dropwise at 25 ° C. or lower, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, 100 mL of diethyl ether and 100 mL of distilled water were added, and the mixture was stirred at room temperature for 10 minutes, and then the collected organic layer was concentrated under reduced pressure to obtain a liquid obtained by column chromatography (developing solvent; ethyl acetate /). Purification was carried out through n-hexane = 1/8) to obtain 12.2 g (yield 81.3%) of the brown solid compound (1).

^{1 1 1} H NMR data (δ ppm; CDCl ₃ ): 1.01 (m, 6H), 1.31 (m, 4H), 1.82 (m, 4H), 7.25-7.97 (m, 8H) ),
MS (m / e): 250

Synthesis 1-2) Synthesis of 1- (9,9-dipropyl-9H-fluorene-2-yl) -1-octanone (2)

After dissolving 10.0 g of compound (1) synthesized from Synthesis 1-1 in 80 mL of dichloromethane, cooling to 5 ° C or lower, 9.0 g of aluminum chloride was added, and then 5.8 g of n-octanoyl chloride was added at 5 ° C. The mixture was added dropwise below and stirred at room temperature for 2 hours. Then, 80.0 g of ice water was gradually added, and the mixture was stirred for 30 minutes. Then, the recovered organic layer was concentrated under reduced pressure, and the obtained solid was purified by column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Then, 11.6 g (yield 76.9%) of the brown compound (2) was obtained.
^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.97 (m, 6H), 1.25 to 1.32 (m, 12H), 1.51 (m, 2H), 1.87 (m, 4H) 2.87 (t, 2H), 7.25-7.97 (m, 7H),
MS (m / e): 376

Synthesis 1-3) Synthesis of 1- (9,9-dipropyl-9H-fluorene-2-yl) -1,2-octanedione-2-oxime (3)

10.0 g of the compound (2) synthesized in Synthesis 1-2 was dissolved in 100 mL of tetrahydrofuran, 0.3 g of isoamyl nitrite and 45 mL of hydrochloric acid gas were added, and the mixture was stirred at 10 ° C. for 6 hours. After completion of the reaction, 100 mL of diethyl ether and 100 mL of distilled water were added, and the mixture was stirred at room temperature for 10 minutes, and then the collected organic layer was concentrated under reduced pressure to obtain a liquid obtained by column chromatography (developing solvent; ethyl acetate /). Purification through n-hexane = 1/8) gave 6.0 g (yield 55.8%) of the pale yellow solid compound (3).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.89 (m, 9H), 1.25 to 1.47 (m, 10H), 1.51 (m, 2H), 1.87 (m, 4H) , 2.15 (t, 2H), 7.25 to 7.97 (m, 7H), 11.0 (s, 1H),
MS (m / e): 405

Synthesis 1-4) Synthesis of compound 1

After dissolving 5.0 g of the compound (3) synthesized in Synthesis 1-3 in 50.0 g of MC, 1.3 g of acetyl chloride is added at 5 ° C. or lower, and 2.0 g of triethylamine (TEA) is added dropwise at the same temperature. After that, the mixture was stirred for 3 hours. When the reaction is completed, 100 mL of distilled water is added, the mixture is stirred for 10 minutes, and the collected organic layer is concentrated under reduced pressure to obtain a yellow liquid through column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Purification gave 14.9 g of a solid compound (yield 89.2%).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.89 (m, 9H), 1.25 to 1.47 (m, 10H), 1.51 (m, 2H), 1.87 (m, 4H) , 2.15 (t, 2H), 2.23 (s, 3H), 7.25-8.1 (m, 7H),
MS (m / e): 447

[Example 2] Synthesis of 1- (9,9-dipropyl-9H-fluorene-2-yl) -1,2-nonandion-2-oxime-O-acetate compound 2 Synthesis 2-1) 1- (9, Synthesis of 9-dipropyl-9H-fluorene-2-yl) -1-nonanone (4)

After dissolving 10.0 g of the compound (1) synthesized from Synthesis 1-1 in 80 mL of dichloromethane, cooling to 5 ° C. or lower, 9.0 g of aluminum chloride was added, and then 6.3 g of n-octanoyl chloride was added at 5 ° C. The mixture was added dropwise below and stirred at room temperature for 2 hours. Then, 80.0 g of ice water was gradually added, and the mixture was stirred for 30 minutes. Then, the recovered organic layer was concentrated under reduced pressure, and the obtained solid was purified by column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Then, 13.1 g (yield 83.7%) of the brown solid compound (4) was obtained.

^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.97 (m, 6H), 1.25 to 1.32 (m, 14H), 1.51 (m, 2H), 1.87 (m, 4H) 2.93 (t, 2H), 7.25-7.97 (m, 7H),
MS (m / e): 390

Synthesis 2-2) Synthesis of 1- (9,9-dipropyl-9H-fluorene-2-yl) -1,2-nonandion-2-oxime (5)

10.0 g of the compound (5) synthesized in Synthesis 2-1 was dissolved in 100 mL of tetrahydrofuran, 0.3 g of isoamyl nitrite and 43 mL of hydrochloric acid gas were added, and the mixture was stirred at 10 ° C. for 6 hours. After completion of the reaction, 100 mL of diethyl ether and 100 mL of distilled water were added, and the mixture was stirred at room temperature for 10 minutes, and then the collected organic layer was concentrated under reduced pressure to obtain a liquid obtained by column chromatography (developing solvent; ethyl acetate / Purification through n-hexane = 1/8) gave 6.0 g (yield 56.1%) of the pale yellow solid compound (5).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.89 (m, 9H), 1.25 to 1.31 (m, 10H), 1.51 (m, 2H), 1.87 (m, 4H) , 2.11 (t, 2H), 7.25-7.97 (m, 7H), 11.0 (s, 1H),
MS (m / e): 405

Synthesis 2-3) Synthesis of compound 2

After dissolving 5.0 g of the compound (5) synthesized in Synthesis 2-3 in 50.0 g of MC, 1.3 g of acetyl chloride was added at 5 ° C. or lower, and 2.0 g of triethylamine was added dropwise at the same temperature. The mixture was stirred for 3 hours. When the reaction is completed, 100 mL of distilled water is added, the mixture is stirred for 10 minutes, and the collected organic layer is concentrated under reduced pressure to obtain a yellow liquid through column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Purification was performed to obtain 25.0 g of a solid compound (yield 91.7%).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.89 (m, 9H), 1.25 to 1.31 (m, 10H), 1.49 (m, 2H), 1.84 (m, 4H) , 2.11 (t, 2H), 2.21 (s, 3H), 7.25-7.97 (m, 7H),
MS (m / e): 461

[Example 3] 1- (9H-fluorene-2-yl) -3-cyclopentyl-1,2-propandion-2-oxime-O-acetate compound 3 synthesis Synthesis 3-1) 1- (9H-fluorene) -2-yl) -3-cyclopentyl-1-propanone (6) synthesis

After dissolving 10.0 g of fluorene in 80 mL of dichloromethane, cooling to 5 ° C or lower, adding 9.0 g of aluminum chloride, 8.8 g of 3-cyclopentylpropionyl chloride is added dropwise at 5 ° C or lower, and the mixture is stirred at room temperature for 2 hours. did. Then, 80.0 g of ice water was gradually added, and the mixture was stirred for 30 minutes. Then, the recovered organic layer was concentrated under reduced pressure, and the obtained solid was purified by column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Then, 12.6 g (yield 72.2%) of the brown solid compound (6) was obtained.

^{1 1} H NMR (δ ppm; CDCl ₃ ): 1.42 (m, 3H), 1.59 to 1.91 (m, 8H), 2.97 (t, 2H) 4.14 (s, 2H), 7.25-8.20 (m, 7H),
MS (m / e): 290

Synthesis 3-2) Synthesis of 1- (9H-fluorene-2-yl) -3-cyclopentyl-1,2-propandion-2-oxime (7)

10.0 g of the compound (6) synthesized in Synthesis 3-1 was dissolved in 100 mL of tetrahydrofuran, 0.4 g of isoamyl nitrite and 54 mL of hydrochloric acid gas were added, and the mixture was stirred at 5 ° C. for 6 hours. After completion of the reaction, 100 mL of diethyl ether and 100 mL of distilled water were added, and the mixture was stirred at room temperature for 10 minutes, and then the collected organic layer was concentrated under reduced pressure to obtain a liquid obtained by column chromatography (developing solvent; ethyl acetate /). Purification was carried out through n-hexane = 1/8) to obtain 5.8 g (yield 53.0%) of the solid compound (7).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 1.52 to 1.94 (m, 9H), 2.07 (m, 2H), 4.14 (s, 2H), 7.25-8.15 ( m, 7H), 11.0 (s, 1H),
MS (m / e): 319

Synthesis 3-3) Synthesis of compound 3

After dissolving 5 g of compound (7) synthesized in Synthesis 3-2 in 50.0 g of MC, 1.6 g of acetyl chloride was added at 5 ° C. or lower, and 2.5 g of triethylamine was added dropwise at the same temperature for 3 hours. Stirred. When the reaction is completed, 100 mL of distilled water is added, the mixture is stirred for 10 minutes, and the collected organic layer is concentrated under reduced pressure to obtain a yellow liquid through column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Purification gave 35.1 g of the compound (yield 90.4%).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 1.52 to 1.94 (m, 9H), 2.23 (s, 3H), 4.13 (s, 2H), 7.25 to 8.15 ( m, 7H),
MS (m / e): 361

[Example 4] Synthesis of 1- (9,9-dimethyl-9H-fluorene-2-yl) -3-cyclopentyl-1,2-propandion-2-oxime-O-acetate compound 4 Synthesis 4-1) Synthesis of 1- (9,9-dimethyl-9H-fluorene-2-yl) -3-cyclopentyl-1-propanone (8)

After dissolving 5.0 g of 9,9-dimethyl-9H-fluorene in 40 mL of dichloromethane, cooling to 5 ° C or lower, adding 3.8 g of aluminum chloride, 3.7 g of 3-cyclopentyl propionyl chloride is dropped at 5 ° C or lower. The mixture was added and stirred at room temperature for 2 hours. Then, 40.0 g of ice water was gradually added, and the mixture was stirred for 30 minutes. Then, the recovered organic layer was concentrated under reduced pressure, and the obtained solid was purified by column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Then, 6.7 g (yield 81.5%) of a brown solid compound (8) was obtained.

^{1 1} H NMR (δ ppm; CDCl ₃ ): 1.42 (m, 3H), 1.67 to 1.92 (m, 14H), 2.98 (t, 2H), 7.25 to 8.02 ( m, 7H),
MS (m / e): 318

Synthesis 4-2) Synthesis of 1- (9,9-dimethyl-9H-fluorene-2-yl) -3-cyclopentyl-1,2-propandion-2-oxime (9)

5.0 g of the compound (8) synthesized in Synthesis 4-1 was dissolved in 50 mL of tetrahydrofuran, 0.2 g of isoamyl nitrite and 25 mL of hydrochloric acid gas were added, and the mixture was stirred at 5 ° C. for 6 hours. After completion of the reaction, 50 mL of diethyl ether and 50 mL of distilled water were added, and the mixture was stirred at room temperature for 10 minutes, and then the collected organic layer was concentrated under reduced pressure to obtain a liquid obtained by column chromatography (developing solvent; ethyl acetate /). Purification through n-hexane = 1/8) gave 2.8 g (yield 50.8%) of the white solid compound (9).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 1.67 to 1.92 (m, 15H), 2.04 (d, 1H), 2.98 (t, 2H), 7.27 to 8.09 ( m, 7H), 11.02 (s, 1H),
MS (m / e): 347

Synthesis 4-3) Synthesis of compound 4

After dissolving 2.5 g of compound (9) synthesized in Synthesis 4-2 in 25.0 g of MC, 0.8 g of acetyl chloride was added at 5 ° C. or lower, and 1.2 g of triethylamine was added dropwise at the same temperature. The mixture was stirred for 3 hours. When the reaction is completed, 50 mL of distilled water is added, the mixture is stirred for 10 minutes, and the collected organic layer is concentrated under reduced pressure to obtain a yellow liquid through column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Purification gave 42.4 g of the compound (yield 86.2%).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 1.67 to 1.92 (m, 15H), 2.04 (d, 1H), 2.21 (s, 3H), 7.27 to 8.09 ( m, 7H),
MS (m / e): 389

[Example 5] Synthesis of 1- (9,9-dipropyl-9H-fluorene-2-yl) -3-cyclopentyl-1,2-propanedione-2-oxime-O-acetate compound 5 Synthesis 5-1) Synthesis of 1- (9,9-dipropyl-9H-fluorene-2-yl) -3-cyclopentyl-1-propanone (15)

After dissolving 10.0 g of compound (1) synthesized from Synthesis 1-1 in 80 mL of dichloromethane, cooling to 5 ° C or lower, 9.0 g of aluminum chloride was added, and then 5.8 g of n-octanoyl chloride was added at 5 ° C. The mixture was added dropwise below and stirred at room temperature for 2 hours. Then, 80.0 g of ice water was gradually added, and the mixture was stirred for 30 minutes. Then, the recovered organic layer was concentrated under reduced pressure, and the obtained solid was purified by column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Then, 11.6 g (yield 77.2%) of the reddish brown compound (10) was obtained.

^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.91 (m, 6H), 1.31 to 1.42 (m, 7H), 1.64 to 1.92 (m, 8H), 2.97 ( t, 2H), 7.25-8.17 (m, 7H),
MS (m / e): 374

Synthesis 5-2) Synthesis of 1- (9,9-dipropyl-9H-fluorene-2-yl) -3-cyclopentyl-1,2-propanedione-2-oxime (11)

10.0 g of the compound (10) synthesized in Synthesis 5-1 was dissolved in 100 mL of tetrahydrofuran, 0.3 g of isoamyl nitrite and 45 mL of hydrochloric acid gas were added, and the mixture was stirred at 10 ° C. for 6 hours. After completion of the reaction, 100 mL of diethyl ether and 100 mL of distilled water were added, and the mixture was stirred at room temperature for 10 minutes, and then the collected organic layer was concentrated under reduced pressure to obtain a liquid obtained by column chromatography (developing solvent; ethyl acetate / Purification through n-hexane = 1/8) gave 6.5 g (yield 60.1%) of the brown solid compound (11).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.89 (m, 6H), 1.31 (m, 4H), 1.62 to 1.91 (m, 9H), 2.03 (t, 2H) , 7.25-8.17 (m, 7H), 11.1 (s, 1H),
MS (m / e): 403

Synthesis 5-3) Synthesis of compound 5

After dissolving 5.0 g of the compound (11) synthesized in Synthesis 5-2 in 50.0 g of MC, 1.3 g of acetyl chloride was added at 5 ° C. or lower, and 2.0 g of triethylamine was added dropwise at the same temperature. The mixture was stirred for 3 hours. When the reaction is completed, 100 mL of distilled water is added, the mixture is stirred for 10 minutes, and the collected organic layer is concentrated under reduced pressure to obtain a yellow liquid through column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Purification gave 54.7 g of a solid compound (yield 85.9%).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.89 (m, 6H), 1.31 (m, 4H), 1.62 to 1.91 (m, 13H), 2.03 (t, 2H) 2.21 (s, 3H), 7.25-8.17 (m, 7H),
MS (m / e): 445

[Example 6] Synthesis of 1- (9,9-dipropyl-9H-fluoren-2-yl) -3-cyclopentyl-1,2-propanedione-2-oxime-O-benzoic acid compound 6 Synthesis 6-1 ) Synthesis of compound 6

After dissolving 5.0 g of the compound (11) synthesized in Synthesis 5-2 in 50.0 g of MC, 2.3 g of benzoyl chloride was added at 5 ° C. or lower, and 2.0 g of triethylamine was added dropwise at the same temperature. The mixture was stirred for 3 hours. When the reaction is completed, 100 mL of distilled water is added, the mixture is stirred for 10 minutes, and the collected organic layer is concentrated under reduced pressure to obtain a yellow liquid through column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Purification was performed to obtain 65.6 g of the compound (yield 89.4%).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.89 (m, 6H), 1.31 (m, 4H), 1.62 to 1.91 (m, 13H), 2.05 (t, 2H) 2.21 (s, 3H), 7.25-8.14 (m, 12H),
MS (m / e): 507

[Example 7] Synthesis of 1- (9,9-dipropyl-9H-fluorene-2-yl) -4-cyclopentyl-1,2-butandion-2-oxime-O-acetate compound 7 Synthesis 7-1) 1 -(9,9-Dipropyl-9H-fluorene-2-yl) -4-cyclopentyl-1-butanone (12) synthesis

After dissolving 5.0 g of compound (1) synthesized from Synthesis 1-1 in 40 mL of dichloromethane, cooling to 5 ° C or lower, adding 4.5 g of aluminum chloride, 3.2 g of n-octanoyl chloride is added at 5 ° C. The mixture was added dropwise below and stirred at room temperature for 2 hours. Then, 40.0 g of ice water was gradually added, and the mixture was stirred for 30 minutes. Then, the recovered organic layer was concentrated under reduced pressure, and the obtained solid was purified by column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Then, 6.3 g (yield 80.8%) of the reddish brown compound (12) was obtained.

^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.91 (m, 6H), 1.21 to 1.44 (m, 9H), 1.71 to 1.92 (m, 4H), 2.97 ( t, 2H), 7.25-8.17 (m, 7H),
MS (m / e): 388

Synthesis 7-2) Synthesis of 1- (9,9-dipropyl-9H-fluorene-2-yl) -4-cyclopentyl-1,2-butandion-2-oxime (13)

5.0 g of the compound (12) synthesized in Synthesis 7-1 was dissolved in 50 mL of tetrahydrofuran, 0.2 g of isoamyl nitrite and 47 mL of hydrochloric acid gas were added, and the mixture was stirred at 10 ° C. for 6 hours. After completion of the reaction, 50 mL of diethyl ether and 10 mL of distilled water were added, and the mixture was stirred at room temperature for 10 minutes, and then the collected organic layer was concentrated under reduced pressure to obtain a liquid obtained by column chromatography (developing solvent; ethyl acetate /). Purification was carried out through n-hexane = 1/8) to obtain 3.3 g (yield 61.7%) of the brown solid compound (13).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.90 (m, 6H), 1.31-1.44 (m, 7H), 1.65-1.92 (m, 12H), 2.13 ( t, 2H), 7.25 to 8.12 (m, 7H), 11.0 (s, 1H),
MS (m / e): 417

Synthesis 7-3) Synthesis of compound 7

After dissolving 3.0 g of the compound (13) synthesized in Synthesis 7-2 in 30.0 g of MC, 0.8 g of acetyl chloride was added at 5 ° C. or lower, and 1.2 g of triethylamine was added dropwise at the same temperature. The mixture was stirred for 3 hours. When the reaction is completed, 30 mL of distilled water is added, the mixture is stirred for 10 minutes, and the collected organic layer is concentrated under reduced pressure to obtain a yellow liquid through column chromatography (developing solvent; ethyl acetate / n-hexane = 1/8). Purification gave 72.8 g of a solid compound (yield 84.2%).

^{1 1} H NMR (δ ppm; CDCl ₃ ): 0.90 (m, 6H), 1.31-1.44 (m, 7H), 1.65-1.92 (m, 12H), 2.12 ( t, 2H), 2.2 (s, 3H), 7.25-8.12 (m, 7H),
MS (m / e): 459

[Comparative Example 1] Synthesis of Compound 8 The following compound 8 was synthesized using a precursor obtained by reacting n-propyl bromide with fluorene by applying the method described in Example 1.
Compound 8 (Comparative Example 1)

[Comparative Example 2] Compound 9
The commercialized OXE-01 was designated as Comparative Example 2.
Compound 9 (Comparative Example 2)

The thermal decomposition temperature, maximum absorption wavelength, gram extinction coefficient, and solubility of the compounds of Examples 1 to 7 and Comparative Examples 1 to 2 were evaluated.

Experimental Example 1: Use of the thermal decomposition temperature rating PerkinElmer TGA (Pyris 1) to measure the thermal decomposition temperature (10 ° C. / 10 _{min, N} 2).

Experimental Example 2: Evaluation of maximum absorption wavelength and gram extinction coefficient
It was measured by dissolving it in acetonitrile at a concentration of 20 ppm using a Shimadzu UV-3600 UV-VIS-NIR spectrophotometer.

Experimental Example 3: Evaluation of solubility The evaluation was made at 20 ° C. to the extent that it was dissolved in 20 g of PGMEA.

From the above results, the thermal decomposition temperature of the compound of the example is significantly higher than that of the compound 8 (Comparative Example 1) and the currently commercialized OXE-01 (Comparative Example 2) having the structure referred to in the existing literature. Because it is high, it can be seen that it has excellent thermal stability. In addition, since it has excellent solubility and a high gram absorption coefficient at the maximum absorption wavelength, it can be confirmed that it has excellent characteristics as compared with existing photoinitiators.

[Manufacturing Example 1] Production of a blue negative photosensitive resin composition using Compounds 1 to 7 of Examples <Production of blue dispersion liquid (A)>
Solvent Propylene glycol monomethyl ether acetate (PGMEA) 80 g, blue pigment pigment blue 15: 612 g, dispersant 4 g (BYK Disperbyk-163), alkali-soluble resin (acrylate-based) 4 g, and then using a high-speed stirrer. After stirring for 2 hours, 0.3 mm zirconia beads were added and stirred at a speed of 8 m / s for 3 hours using a bead mill manufactured by Nets to obtain a blue pigment dispersion (A).

<Manufacturing of alkaline developable resin (B)>
231 g of epoxy bisphenol fluorene, 72 g of acrylic acid, 0.1 g of tetra-n-butylammonium bromide and 250 g of PgMEA were placed in the reaction vessel, and the mixture was stirred at 120 ° C. for 22 hours while performing air bubbling. After that, the reaction solution was cooled to 90 ° C., 60 g of bisphenol anhydride was added, and the mixture was stirred at 120 ° C. for 8 hours. Then, after cooling to 90 ° C., 20 g of tetrahydrophthalic anhydride and 100 g of PGAMEA were added, and additional stirring was carried out at 120 ° C. for 6 hours. After that, it was cooled to room temperature to obtain an alkaline developable resin (B). At this time, the solid content was 50%, Mn = 3500, and the acid value (solid content) was 95.3 mg KOH / g.

<Manufacturing of alkaline developable resin (C)>
84.5 g of cinnamyl alcohol, 76.6 g of triethylamine, 0.14 g of a polymerization inhibitor, and 422 g of the solvent dichloromethane were added to the reaction vessel, and then 106.7 g of methacrylate was gradually added while maintaining room temperature. After the charging was completed, the temperature was raised to 40 ° C. and then kept for 24 hours. After that, water was added to proceed with extraction and concentration to obtain cinnamyl methacrylate. 96.8 g of cinnamaldehyde methacrylate, 33.3 g of methacrylic acid, 12 g of styrene, 11.0 g of AIBN, and 230 g of PGMEA were added and held at 85 ° C. for 6 hours to obtain an alkali developable resin (C). At this time, the solid content was 40%, Mn = 8,800, and the acid value (solid content) was 160 mg KOH / g.

<Manufacturing of blue photosensitive resin composition>
In 21.2 g of the dispersion liquid (A), 6.6 g of the alkaline developable resin (B), 2.8 g of the alkaline developable resin (C), 0.6 g of dipentaerythritol penta and hexaacrylate, and a photopolymerization initiator (Compound 1). Or compound 7) 1.5 g and 0.05 g of a surfactant were added and stirred, and PGMEA was added so that the final solid content concentration became 20% by weight to obtain a blue negative photosensitive resin composition. ..

[Production Example 2] Production of Blue Negative Photosensitive Resin Composition Using Compound of Comparative Example Light such as compound 8 (Comparative Example 1) and compound 9 (Comparative Example 2) below is used instead of compound 1 to compound 7. A blue negative photosensitive resin composition was produced using the same method as in Production Example 1 except that the compound was produced using a polymerization initiator.
Comparative Example 1, Comparative Example 2

Experimental Example 4: Evaluation of Required Minimum Exposure, Line Width, Luminance, and Adhesion After coating the substrate with the photosensitive resin composition produced from Production Example 1 and Production Example 2, the minimum exposure, line width, brightness, and Adhesion was evaluated.

[Minimum required exposure]
The sensitivity was evaluated with the minimum irradiation exposure amount at which the film thickness after development is 80% or more of the film thickness of the coating film after coating as the required minimum exposure amount.
[Line width]
When the same 60 mJ / cm ² is exposed and developed, it means the width of the generated pattern, and the wider the line width, the higher the sensitivity.
[Luminance]
After development, measurement was performed using a color difference meter (CA-310, Konica Minolta).
[Adhesion (resolution)]
After exposing and developing the same 60 mJ / cm ² , the smallest mask line width of the remaining pattern was measured. When it is 10 μm or less, it is indicated as ◯, when it is 15 μm or less, it is indicated as Δ, and when it is 20 μm or less, it is indicated as X.

According to Table 4, the blue negative photosensitive resin composition produced by the production example 1 containing the compounds of Examples 1 to 7 is excellent in that it has high sensitivity and excellent adhesion and the like. It can be seen that it has physical properties.

[Production Example 3] Production of a black negative photosensitive resin composition using the compound of Example (for black matrix)
19.8 g of alkali-developable resin (B), 5 g of dipentaerythritol penta and hexaacrylate, and compound 1 of compound 1 to compound 7 as a photopolymerization initiator in 45 g of a carbon black dispersion (solid content 22% in PGMEA) solution. 0.0 g and 0.05 g of a surfactant were added and stirred, and PGMEA was added so that the final solid content concentration became 20% by weight to obtain a black negative photosensitive resin composition.

[Production Example 4] Production of Black Negative Photosensitive Resin Composition Using Compound of Comparative Example Compound 8 to Compound 9 of Comparative Example was used as a photopolymerization initiator instead of Compound 1 to Compound 7 of Example. Except for this, a black negative photosensitive resin composition was produced using the same method as in Production Example 3.

Experimental Example 5: Evaluation of Line Width, Adhesion and Developability After coating the substrate with the black negative photosensitive resin composition produced from Production Example 3 and Production Example 4, the minimum exposure amount, line width, brightness and adhesion Was evaluated.

[Line width]
When the same 40 mJ / cm ² is exposed and developed, it means the width of the generated pattern, and the wider the line width, the higher the sensitivity.
[Adhesion (resolution)]
After exposing the same 40 mJ / cm ² and developing for the same time (33 seconds), the smallest mask line width of the remaining pattern was measured. When it is 10 μm or less, it is indicated as ◯, when it is 15 μm or less, it is indicated as Δ, and when it is 20 μm or less, it is indicated as X.
[Developability]
It was confirmed by the melting start time (seconds; brake point) at the time of development. It can be said that the shorter the brake point, the better the developability.

According to Table 5, the black negative photosensitive resin composition containing the photoinitiator of Compound 1 to Compound 7 according to the present invention has excellent physical properties such as excellent adhesion and developability. I understand.

[Production Example 5] Production of a transparent negative photosensitive resin composition using Compounds 1 to 7 of Examples (for insulating film)
12.0 g of alkaline developable resin (B), 24.0 g of alkaline developable resin (C), 41 g of dipentaerythritol penta and hexaacrylate, 72.0 g of compound 1 to 7 as a photopolymerization initiator, surface activity. 0.2 g of the agent was added and stirred, and PGMEA was added so that the final solid content concentration became 20% by weight to obtain a transparent negative photosensitive resin composition.

[Production Example 6] Production of a transparent negative photosensitive resin composition using Compounds 8 and 9 of Comparative Examples (for insulating film)
Same as Production Example 5 except that Compound 8 and Compound 9 (Comparative Example 1 and Comparative Example 2) of Comparative Example were used as photopolymerization initiators in place of the compounds of Examples of Compounds 1 to 7. A transparent negative photosensitive resin composition was produced using the method.

Experimental Example 6: Evaluation of Remaining Film Ratio and Resolving Power The residual film ratio and resolving power of the film formed by coating the substrate with the transparent negative photosensitive resin composition produced from Production Example 5 and Production Example 6 and then exposing the film. evaluated.

[Residual film ratio]
The ratio of the film thickness before exposure to the film thickness after exposure and development is defined as the residual film ratio. The higher the residual film ratio, the higher the sensitivity.
[Resolution]
After exposing and developing the same 60 mJ / cm ² , the minimum pattern size was defined as the resolution.

According to Table 6, the transparent negative photosensitive resin composition containing the photoinitiator of Compound 1 to Compound 7 produced in Production Example 5 has excellent physical properties such as excellent resolving power and developability. I understand.
Those skilled in the art can make various applications and modifications within the scope of the present invention based on the above contents.

Since the oxime ester compound according to the present invention is excellent in storage stability, polymerization does not occur in the storage state, and the polymerizable composition can be efficiently polymerized in a short time. In addition, since it has excellent solubility in PGMEA, which is a solvent mainly used for color filters, it has excellent transparency and chemical resistance when applied as a photoinitiator of a photoresist composition, and is used in the LCD manufacturing process. When applied to certain column spacers, overcoats, organic insulating films, color filters, and black matrices, there is almost no change in the brightness of the resin composition and the transparency of the resin, which minimizes quality problems and provides thermal stability. It is possible to produce an excellent photopolymerization initiator and a photosensitive composition.

Claims (8)

Oxime ester compound represented by the following chemical formula 1' :
Chemical formula 1'
In the above formula
R ₁ is a methyl or phenyl group
R ₂ and R ₃ are independently selected from hydrogen, methyl group, ethyl group, propyl group, and butyl group, respectively.
n is, Ru integer der of 2-4. The following compounds
The oxime ester compound according to claim 1, which is selected from the group consisting of. A photopolymerization initiator comprising the oxime ester compound according to claim 1 or 2 as an active ingredient. A photosensitive resin composition comprising the photopolymerization initiator according to claim 3 , a compound having an ethylene-based unsaturated bond, and a binder resin. The fourth aspect of claim 4 , wherein the photosensitive resin composition is a negative photosensitive resin composition used for producing a color filter, a black matrix, an organic insulating film, a column spacer, or an overcoat. Photosensitive resin composition. The photosensitive resin composition contains 0.01 to 10% by weight of an oxime ester compound of chemical formula 1' , 0.001 to 50% by weight of a polymerizable compound having an ethylenically unsaturated bond, 20 to 80 % by weight of a solvent, and a bond. The photosensitive resin composition according to claim 4 , further comprising 5 to 60% by weight of the agent resin. The photosensitive resin composition The photosensitive resin composition according to claim 5, characterized in that the black matrix further contains carbon black. The photosensitive resin composition according to claim 5 , wherein the photosensitive resin composition is for a color matrix further containing a coloring material.