KR20170035727A - Oxime ester compound having improved heat stability, photopolymerization initiator and photoresist composition comprising the same - Google Patents

Abstract

The present invention provides oxime ester compound represented by a following formula (1), which is suitable for a photo initiator for a high-brightness material and a transparent material, and has excellent thermal stability and solubility for an organic solvent, and photopolymerization initiator containing the oxime ester compound. [FORMULA 1], R1 ~ R3 and n and m are respectively defined in the present specification.

Description

An oxime ester compound having excellent heat stability, a photopolymerization initiator containing the same, and a photosensitive resin composition having improved thermal stability, photopolymerization initiator and photoresist composition,

The present invention relates to an oxime ester compound and a photopolymerization initiator using the oxime ester compound. More particularly, the present invention relates to a oxime ester compound having a novel structure useful for manufacturing a photosensitive resin composition which maintains high brightness, is excellent in thermal stability, And a photopolymerization initiator comprising the same.

The photosensitive composition is prepared by adding a photopolymerization initiator to a binder resin and a polymerizable compound having an ethylenically unsaturated bond. Since the photosensitive composition can be polymerized and cured by irradiating light of 365 to 435 nm, the inkjet ink, And is widely used in flat panel display (FPD) TVs and LCD TVs in recent years.

LCD manufacturing requires a large number of optical technologies and a large number of electronic components. One of the most important parts of LCD manufacturing is a color filter having red, green, blue and black pixels. The color filter is manufactured by a photolithography method which utilizes a phenomenon in which the solubility is reduced according to a polymerization reaction by light, and a photopolymerization initiator is applied to a photosensitive composition for each color used in a color filter.

The photosensitive resin composition is important in high production efficiency, photospeed, sensitivity to light-cure with minimal exposure, 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 increases, the sensitivity, developability, resolution, and adhesion of the photosensitive resin composition deteriorate. In addition to the deterioration of the productivity, It is known that it can not be done. That is, a color filter is required to have high sensitivity and high resolution at a high concentration, and a photosensitive resin composition for a black matrix is also required to be able to exhibit high sensitivity and high resolution under a condition of a thin film, high light intensity (high concentration).

In addition, in the case of conventional products, there is a limit to its application due to a low thermal stability problem, and therefore, there is a need for a photoinitiator having improved thermal stability.

Therefore, there is a high demand for an oxime ester compound having a novel structure capable of fundamentally solving such a problem, and a negative type photosensitive resin composition containing the same.

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and the technical problems required from the past.

Specifically, the inventors of the present application have conducted intensive research and various experiments, and have found that the oxime ester compound having a novel structure as described below has superior transparency and thermal stability as compared with the initiator of the prior art, It has been found that when applied to a resin composition, there is little change in luminance and a change in transparency of a resin, and excellent resolution, developability and adhesion, and excellent thermal stability. Thus, the present invention has been accomplished.

The present invention provides an oxime ester compound represented by the following formula (1).

[Chemical Formula 1]

In the above formula,

R ₁ is a methyl or phenyl group,

R ₂ and R ₃ are each selected from hydrogen, a methyl group, an ethyl group, a propyl group and a butyl group,

n is an integer of 1 to 4,

m is an integer of 0 to 6,

Provided that when n is 1, m is an integer of 1 to 6;

The present invention also provides a photopolymerization initiator comprising the oxime ester compound as an active ingredient.

The present invention also provides a photosensitive resin composition comprising a binder resin, a compound having an ethylenically unsaturated bond and the photopolymerization initiator.

Since the oxime ester compound according to the present invention has excellent storage stability, polymerization is not caused in the preserved state, and the polymerizable composition can be efficiently polymerized in a short time. In addition, since it is excellent in solubility in PGMEA (a solvent used mainly for color filters), it is superior in transparency and chemical resistance when applied as a photo-initiator of a photoresist composition. In addition, There can be obtained a photopolymerization initiator and a photosensitive composition which are excellent in thermal stability and which can minimize the quality problems due to little change in brightness of the resin composition and transparency of the resin when applied to an overcoat, an organic insulating film, a color filter and a black mattress have.

The present invention provides an oxime ester compound represented by the following formula (1).

[Chemical Formula 1]

In the above formula,

R ₁ is a methyl or phenyl group,

R ₂ and R ₃ are each selected from hydrogen, a methyl group, an ethyl group, a propyl group and a butyl group,

n is an integer of 1 to 4,

m is an integer of 0 to 6,

Provided that when n is 1, m is an integer of 1 to 6;

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

The oxime used as a starting material in the preparation of the oxime ester compound according to the present invention may be a standard chemical textbook (for example, J. March, Advanced Organic chemistry, 4 ^th edition, Wiley Interscience, 1992) or a professional monograph For example, SR Sandler & W. Karo, Organic functional group preparations, Vol.3, Academic Press.

The present invention provides a photopolymerization initiator comprising the oxime ester compound as an active ingredient.

The photopolymerization initiator according to the present invention has a higher sensitivity than conventional initiators and is excellent in resolution, developability and adhesion, and has excellent solubility in PGMEA, which is a solvent mainly used in the LCD manufacturing process. Thus, And can be used throughout the photocuring industry such as black matrix, column spacer, organic insulating film, and overcoat.

The present invention also provides a photosensitive resin composition comprising a binder resin, a compound having an ethylenically unsaturated bond and the photopolymerization initiator.

The amount of the photopolymerization initiator to be added is not particularly limited, but the oxime ester compound according to the present invention is preferably 1 to 50 parts by weight, more preferably 1 to 50 parts by weight, per 100 parts by weight of the polymerizable compound solid component having an ethylenic unsaturated bond 5 to 30 parts by weight.

The compound having an ethylenically unsaturated bond is a compound used in a conventional photosensitive resin composition, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl Acrylate, trimethylolpropane tri (meth) acrylate, triethylene glycol (meth) acrylate, pentaerythritol tetra (meth) acrylate, (Meth) acrylic acid, styrene, acrylonitrile and the like, such as acrylic acid esters and methacrylic acid esters such as dipentaerythritol acrylate, dipentaerythritol acrylate, glycerol (meth) acrylate, melamine (meth) acrylate and epoxy . Further, bisphenol-A type epoxy di (meth) acrylate and bisphenol-fluorene type epoxy di (meth) acrylate are preferable, but not limited thereto.

These ethylenically unsaturated bond-containing compounds may be used singly or in combination of two or more. The compound may be used in an amount of usually 5 to 60% by weight, preferably 10 to 50% by weight based on the total weight of the solid components of the negative photosensitive resin composition according to the present invention. Further, it may be 0.001 to 50% by weight, preferably 0.1 to 7% by weight, based on the total weight of the photosensitive resin composition.

In addition to the oxime ester compound of the present invention, other types of photopolymerization initiators can be used in combination with the negative photopolymerizable resin composition according to the present invention, and other types of photopolymerization initiators can be used together to provide a synergistic effect It may be exercised.

The negative-working photosensitive resin composition containing such a photopolymerization initiator can be used as a high-sensitivity material that efficiently decomposes and efficiently generates radicals even when the sensitizer is not used in combination with light irradiation in a specific wavelength range.

As the photopolymerization initiator usable with the oxime ester compound of the present invention, conventionally known compounds can be used. Preferred examples thereof include benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3'-dimethyl 4-methoxybenzophenone, benzoylbenzoic acid, esters of benzoylbenzoic acid, 4-benzoyl-4'-methyldiphenylsulfide, benzyldimethylketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone , Methyl thioxanthone, ethyl thioxanthone, isopropyl thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, diisopropyl thioxanthone, dimethylaminomethylbenzoate, dimethylaminobenzoic acid isoamyl ester, 1- (1-hydroxycyclohexylphenyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 - (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- Methylbenzoylformate, 2-methyl-1- (4-methylthiophenyl) -2 -morpholinopropane-1-one, 2-benzyl-2-dimethylamino- ) -Butane-1-one, 2.2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'- 4, 5,5'-tetra- (4-methoxyphenyl) bisimidazole, 2,4-bis (trichloromethyl) -6- Triazine, 2,4,6-tris (trichloromethyl) -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- Acetate, 1- (4-methylsulfanylphenyl) butan-1-one oxime-O-acetate, ethanone , 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Shim), but the present invention is not limited thereto.

These photopolymerization initiators may be used singly or in combination of two or more in an optional ratio as required. In the present invention, the photopolymerization initiator may be used in an amount of usually 0.5 to 30% by weight, preferably 1 to 20% by weight based on the total weight of the solid components of the negative photosensitive resin composition according to the present invention. Further, it may be 0.01 to 10% by weight, preferably 0.1 to 7% by weight based on the total weight of the photosensitive resin composition.

As the binder resin, a copolymer of a compound having an unsaturated carboxyl group and 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 being polymerized. 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 mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals, such as? -Carboxypolycaprolactone mono (meth) acrylate, monomethyl (meth) acrylate, ((Meth) acryloyloxy) ethyl succinate, or a mixture thereof. Examples of the above-mentioned monomers include mono-2 - ((meth) acryloyloxy) ethyl phthalate, The compounds having an unsaturated carboxyl group may be used alone or in combination of two or more thereof, but are not limited thereto. Among the compounds having an unsaturated carboxyl group, acrylic acid and methacrylic acid are preferably used because of their excellent copolymerization reactivity and solubility in a developing solution.

The other monomer copolymerizable with the carboxyl group-containing monomer may be used without limitation as long as it is a monomer having a carbon-carbon unsaturated bond. Specifically, aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene; Acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, Unsaturated carboxylate compounds such as acrylate; Unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Vinylcyanide compounds such as acrylonitrile, methacrylonitrile and? -Chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, Methyl-3-acryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, Unsaturated oxetanecarboxylate compounds, and the like. The above-exemplified monomers copolymerizable with the unsaturated carboxyl group-containing compounds may be used singly or in combination of two or more thereof, but are not limited thereto.

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

The binder resin may be a cadmium resin represented by the following general formula (2) which is generally used in the field of black matrix.

(2)

In the general formula (2), Q is a tetravalent organic group and z is an integer of 1 or more representing a repeating unit.

The cardade resin is preferably selected from the group consisting of bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone and bis , Bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane and bis (4-hydroxy- Bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane and bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) methane, bis Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane and 2,2-bis (4-hydroxy- (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxyphenyl) (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9- (3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9- , 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxyphenyl) 3,5-dibromophenyl) fluorene, and the like, but is not limited thereto.

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

The binder resin may be contained in the photosensitive resin composition in an amount of 5 to 60% by weight, preferably 10 to 40% by weight based on the total weight of the solid content of the photosensitive resin composition. If the content of the binder resin is within the above range, a pattern can be formed and the resolution and the residual film ratio can be improved. However, if the binder resin is out of this range, the resolution and retention rate may be decreased.

The photosensitive resin composition according to the present invention may optionally contain thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, tert-butyl catechol, phenothiazine, and the like; Plasticizers; Adhesion promoters; Additive for general use such as filler may be added.

In addition, the photosensitive resin composition according to the present invention may further contain at least one selected from a colorant, an inorganic compound, a dispersant, and a silane coupling agent.

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

As the pigment, for example, nitroso compounds; Nitro compounds; Azo compounds; Diazo compounds; Xanthene compounds; Quinoline compounds; Anthraquinone compounds; Coumarin compounds; Phthalocyanine compounds; Isoindolinone compounds; Isoindoline compounds; Quinacridone compounds; Anthanthrone compounds; Perinone compounds; Perylene compounds; Diketopyrrolopyrrole compounds; Thioindigo compounds; Dioxazine compounds; Triphenylmethane compounds; Quinophthalone compounds; Naphthalene tetracarboxylic acid; Azo dyes, metal complex compounds of cyanine dyes; Lake pigments; A carbon black obtained by a furnace method, a channel method or a thermal method, or carbon black such as acetylene black, Ketjen black or lamp black; The carbon black is adjusted or coated with an epoxy resin, the carbon black is dispersed in a solvent in advance in a solvent to adsorb a resin of 20 to 200 mg / g, an acidic or alkaline surface-treated carbon black, A DBP oil absorption amount (oil absorption amount) of not more than 90 ml / 100 g, a total oxygen amount calculated from CO and CO ₂ in volatile matter at 950 ° C of not less than 9 m 2 per 100 m 2 of the surface area of carbon black; Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon airgel, fullerene; Aniline black, pigment black 7, titanium black; Cobalt blue, manganese, ferrocyanide, phosphates, cadmium, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc sulfur, Red iron oxide (III)), cadmium red, synthetic iron black, and amber. These pigments may 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 may be preferably 50 to 350 parts by weight, more preferably 100 to 250 parts by weight, based on 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond .

If the amount of the coloring material is included in a preferable range for expressing a desired color in an excessively large amount or less, the negative type photosensitive resin composition having an appropriate color intended by the present invention can not be obtained.

The photosensitive resin composition according to the present invention may further contain an inorganic compound. Examples of the inorganic compound include a composite metal oxide pigment, carbon black, black low-order titanium oxynitride, titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, Ben gala, Metal oxides, metal sulfides, sulfates, metal hydroxides, metal carbonates and the like of chromium oxide, antimony white, iron black, podium, zinc sulfide, cadmium yellow, cadmium red, zinc, manganese violet, cobalt violet, barium sulfate, But are not limited to these. These inorganic pigments may be used singly or in combination of two or more thereof, if necessary. In the negative-working photosensitive resin composition of the present invention, the content of the inorganic compound is preferably 0.1 to 1000 parts by weight, preferably 10 to 800 parts by weight, based on 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond have.

A dispersing agent for dispersing the coloring material and / or the inorganic compound may be added to the photosensitive resin composition of the present invention. The dispersing agent is not limited as long as it can disperse and stabilize the coloring material or the inorganic compound, and a commercially available dispersing agent, for example, BYK series which is a product of Bigkema can be used. A polymer dispersant comprising a basic functional group such as a polyester, a polyether or a polyurethane having a basic functional group, a functional group having a nitrogen atom as a basic functional group and having a nitrogen atom is an amine and / or a quaternary salt thereof and an amine value of 1 to 100 mgKOH / g is preferably used.

In addition, a silane-based coupling agent may be 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 vinylalkoxy-containing silane coupling agent, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (? -Methoxyethoxy) silane and the like can be used. Examples of the silane coupling agent containing (meth) acryloxy include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, and the like can be used. The addition ratio thereof may be 0.01 to 2% by weight, more preferably 0.05 to 0.5% by weight, based on the total weight of the negative photosensitive resin composition.

In the photosensitive resin composition of the present invention, a solvent may be used as needed for viscosity control. Specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether and the like Diethylene glycol dialkyl ethers such as glycol monoalkyl ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cell Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate; alkylene glycol alkyl ether acetates such as methoxybutyl acetate, methoxy Methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, and butanol; alcohols such as benzene, toluene, xylene and mesitylene; ketones such as acetone, , Alcohols such as hexanol, cyclohexanol, ethylene glycol and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone .

The organic solvent having a boiling point of 100 ° C to 200 ° C in the solvents exemplified above in terms of coatability and dryness can be preferably used, and alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate or 3 -Methoxypropionate and the like can be more preferably used. In particular, esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate Can be more preferably used. The solvent may be used alone or in combination of two or more. It is preferable to select the proportion of the solvent so that the resin liquid has a viscosity such that it can be applied to the substrate. Usually, it may be contained in an amount of 10 to 95% by weight, preferably 20 to 80% by weight based on the total weight of the photosensitive resin composition have.

In addition, a certain amount of other additives such as a chain transfer agent, a sensitizer, a surfactant, an antioxidant, and a stabilizer may be added to the photosensitive resin composition according to the present invention within a range that does not impair the physical properties of the resin composition. The amount of such additives to be added can be controlled by those skilled in the art.

By using such a photosensitive resin composition, a color filter, a black matrix, a column spacer, an organic insulating film, an overcoat and the like can be produced.

Specifically, the present invention can provide a color filter comprising the photosensitive resin composition. The negative-type photosensitive resin composition used for such a color filter is, for example, 20 to 30% by weight, preferably 23 to 27% by weight, based on the total weight of solids, 15: 6, For example, it may show blue color including 25% by weight.

The present invention also provides a black matrix comprising the photosensitive resin composition. The negative photosensitive resin composition used in such a black matrix may contain 10 to 15% by weight, preferably 11 to 13% by weight, for example, about 12.4% by weight, based on the total solid weight of carbon black, And black can be displayed.

Hereinafter, the method for these will be described in detail.

The method for producing a color filter and a black matrix of the present invention is a method for producing a color filter and a black matrix by applying the dye-containing negative curable resin composition of the present invention onto a support by a coating method such as spin coating, The layer is exposed through a predetermined mask pattern and developed with a developing solution to form a negative type coloring pattern (image forming step). Further, if necessary, it may include a curing step of curing the formed colored pattern by heating and / or exposure.

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

Examples of the support include soda glass, Pyrex glass, quartz glass and a transparent conductive film adhered to them, photoelectric conversion element substrates used for image pickup elements and the like, for example, silicon substrates used for liquid crystal display devices, , Complementary metal oxide semiconductor (CMOS), and the like. These supports may be formed with black stripes that isolate each pixel.

On the support, a primer layer may be formed on the support in order to improve adhesion with the upper layer, prevent diffusion of the substance, or planarize the surface of the support, if necessary.

Any developer may be used as long as it dissolves the uncured portion of the dye-containing negative curable resin composition of the present invention while the irradiated portion does not dissolve. Specifically, a combination of various organic solvents or an alkaline aqueous solution may be used as the developer. Examples of the organic solvent include the above-mentioned organic solvents 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, Alkaline compounds such as choline, pyrrole, piperidine and 1,8-diazabicyclo- [5.4.0] -7-undecene are dissolved in an amount of 0.001 to 10 mass%, preferably 0.01 to 1 mass% May be used. When a developer composed of such an alkaline aqueous solution is used, it can generally be washed with water after development.

Such a color filter, a black matrix, or a column spacer may be usefully used in a liquid crystal display or a solid-state image pickup device.

The liquid crystal display device may 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,

The solid-state image pickup device can be manufactured by forming the color filter layer of the present invention on a silicon wafer on which a transfer electrode and a photodiode are formed, and then laminating microlenses.

Hereinafter, the content of the present invention will be described with reference to Examples, but the scope of the present invention is not limited thereto.

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

Synthesis 1-1) 9,9-Dipropyl-9 H -Fluorene < / RTI > (1)

Fluorene and 100 mL of tetrahydrofuran, 16.2 g of 1-bromopropane was added dropwise at 25 DEG 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. After stirring at room temperature for 10 minutes, the collected organic layer was concentrated under reduced pressure. The obtained liquid was purified through column chromatography (developing solvent ethyl acetate / n-hexane = 1/8) To obtain 12.2 g (yield 81.3%) of a brown solid compound (1).

¹ H NMR data (? Ppm: CDCl ₃ ): 1.01 (m, 6H), 1.31 (m, 4H), 1.82

MS (m / e): 250

Synthesis 1-2) 1- (9,9-Dipropyl-9 H -Fluoren-2-yl) -1-octanone (2) Synthesis of

10.0 g of the compound (1) synthesized in Synthesis 1-1 was dissolved in 80 mL of dichloromethane, cooled to 5 캜 or lower, and then added with 9.0 g of aluminum chloride. Then, 5.8 g of n-octanoyl chloride was added dropwise at 5 캜 or lower The mixture was stirred at room temperature for 2 hours. Then, 80.0 g of ice water was slowly added thereto, and the mixture was stirred for 30 minutes. The recovered organic layer was concentrated under reduced pressure, and the obtained solid was purified through column chromatography (developing solvent ethyl acetate / n-hexane = 1/8) 11.6 g (yield: 76.9%) was obtained.

^{1 H NMR (δ ppm; CDCl} 3): 0.97 (m, 6H), 1.25 ~ 1.32 (m, 12H), 1.51 (m, 2H), 1.87 (m, 4H), 2.87 (t, 2H), 7.25 ~ 7.97 (m, 7 H)

MS (m / e): 376

Synthesis 1-3) 1- (9,9-Dipropyl-9 H -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 nitrate and 45 mL of hydrochloric acid gas were added, and the mixture was stirred at 10 DEG C for 6 hours. After completion of the reaction, 100 mL of diethyl ether and 100 mL of distilled water were added. After stirring at room temperature for 10 minutes, the collected organic layer was concentrated under reduced pressure. The obtained liquid was purified through column chromatography (developing solvent ethyl acetate / n-hexane = 1/8) 6.0 g (yield: 55.8%) of yellow solid compound (3) was obtained.

¹ H NMR (? Ppm; CDCl ₃ ): 0.89 (m, 9H), 1.25-1.47 (m, 10H), 1.51 (m, 2H) 7.97 (m, 7 H), 11.0 (s, 1 H),

MS (m / e): 405

Synthesis 1-4) Synthesis of Compound 1

5.0 g of the compound (3) synthesized in Synthesis 1-3 was dissolved in 50.0 g of MC, 1.3 g of acetyl chloride was added at 5 ° C or lower, 2.0 g of triethylamine (TEA) was added dropwise at the same temperature, Lt; / RTI > When the reaction was completed, 100 mL of distilled water was added and stirred for 10 minutes. The recovered organic layer was concentrated under reduced pressure, and the resulting yellow liquid was purified through column chromatography (eluent ethyl acetate / n-hexane = 1/8) to obtain 4.9 g (Yield: 89.2%).

¹ H NMR (? Ppm; CDCl ₃ ): 0.89 (m, 9H), 1.25-1.47 (m, 10H), 1.51 (m, 2H), 1.87 s, 3H), 7.25 ~ 8.1 (m, 7H)

MS (m / e): 447

[Example 2] Synthesis of 1- (9,9-dipropyl-9 H -Fluoren-2-yl) -1,2-nonanedione-2-oxime- O Synthesis of acetate compound 2

Synthesis 2-1) 1- (9,9-Dipropyl-9 H -Fluoren-2-yl) -1-butenone (4) Synthesis of

10.0 g of the compound (1) synthesized in Synthesis 1-1 was dissolved in 80 mL of dichloromethane, cooled to 5 캜 or lower, and then added with 9.0 g of aluminum chloride, and then 6.3 g of n-octanoyl chloride was added dropwise at 5 캜 or lower The mixture was stirred at room temperature for 2 hours. Then, 80.0 g of ice water was slowly added thereto and stirred for 30 minutes. The recovered organic layer was concentrated under reduced pressure, and the resulting solid was purified through column chromatography (developing solvent ethyl acetate / n-hexane = 1/8) to obtain a brown solid compound 4 ) (Yield: 83.7%).

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

MS (m / e): 390

Synthesis 2-2) 1- (9,9-Dipropyl-9 H -Fluoren-2-yl) -1,2-nonanedione-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 DEG C for 6 hours. After completion of the reaction, 100 mL of diethyl ether and 100 mL of distilled water were added. After stirring at room temperature for 10 minutes, the collected organic layer was concentrated under reduced pressure. The obtained liquid was purified through column chromatography (developing solvent ethyl acetate / n-hexane = 1/8) 6.0 g (yield: 56.1%) of yellow solid compound (5) was obtained.

¹ H NMR (? Ppm; CDCl ₃ ): 0.89 (m, 9H), 1.25-1.31 (m, 10H) 7.97 (m, 7 H), 11.0 (s, 1 H),

MS (m / e): 405

Synthesis 2-3) Synthesis of Compound 2

5.0 g of the compound (5) synthesized in Synthesis 2-3 was dissolved in 50.0 g of MC, and 1.3 g of acetyl chloride was added thereto at 5 캜 or lower. 2.0 g of triethylamine was added dropwise thereto at the same temperature, followed by stirring for 3 hours. When the reaction was completed, 100 mL of distilled water was added and stirred for 10 minutes. The recovered organic layer was concentrated under reduced pressure, and the resulting yellow liquid was purified through column chromatography (eluent ethyl acetate / n-hexane = 1/8) to obtain 5.0 g (Yield: 91.7%).

¹ H NMR (? Ppm; CDCl ₃ ): 0.89 (m, 9H), 1.25-1.31 (m, 10H), 1.49 (m, 2H), 1.84 s, 3H), 7.25-7.97 (m, 7H)

MS (m / e): 461

[Example 3] 1- (9 H -Fluoren-2-yl) -3-cyclopentyl-1,2-propanedione-2-oxime- O Synthesis of Acetate Compound 3

Synthesis 3-1) 1- (9 H -Fluoren-2-yl) -3-cyclopentyl-1-propanone (6)

Fluorene was dissolved in 80 mL of dichloromethane, and the mixture was cooled to 5 캜 or lower. 9.0 g of aluminum chloride was added thereto, and then 8.8 g of 3-cyclopentylpropanoyl chloride was added dropwise at 5 캜 or lower, followed by stirring at room temperature for 2 hours Respectively. Then, 80.0 g of ice water was slowly added thereto and stirred for 30 minutes. The recovered organic layer was concentrated under reduced pressure, and the resulting solid was purified through column chromatography (developing solvent ethyl acetate / n-hexane = 1/8) to obtain a brown solid compound 6 ) (Yield: 72.2%).

^{1 H NMR (δ ppm; CDCl} 3): 1.42 (m, 3H), 1.59 ~ 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-fluoren-2-yl) -3-cyclopentyl-1,2-propanedione-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 nitrate and 54 mL of hydrochloric acid gas were added, and the mixture was stirred at 5 캜 for 6 hours. After completion of the reaction, 100 mL of diethyl ether and 100 mL of distilled water were added. After stirring at room temperature for 10 minutes, the collected organic layer was concentrated under reduced pressure. The obtained liquid was purified through column chromatography (developing solvent ethyl acetate / n-hexane = 1/8) To obtain 5.8 g (yield: 53.0%) of solid compound (7).

^{1 H NMR (δ ppm; CDCl} 3): 1.52 ~ 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

5 g of the compound (7) synthesized in Synthesis 3-2 was dissolved in 50.0 g of MC, and 1.6 g of acetyl chloride was added thereto at 5 캜 or lower. 2.5 g of triethylamine was added dropwise thereto at the same temperature, followed by stirring for 3 hours. After the reaction was completed, 100 mL of distilled water was added and stirred for 10 minutes. The recovered organic layer was concentrated under reduced pressure, and the resulting yellow liquid was purified by column chromatography (eluent ethyl acetate / n-hexane = 1/8) Yield: 90.4%).

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

MS (m / e): 361

[Example 4] 1- (9,9-dimethyl-9 H -Fluoren-2-yl) -3-cyclopentyl-1,2-propanedione-2-oxime- O - Synthesis of acetate compound 4

Synthesis 4-1) 1- (9,9-Dimethyl-9 H -Fluoren-2-yl) -3-cyclopentyl-1-propanone (8)

9,9-dimethyl-9H-fluorene was dissolved in 40 mL of dichloromethane, cooled to 5 DEG C or lower, and 3.8 g of aluminum chloride was added thereto. Then 3.7 g of 3-cyclopentylpropanoyl chloride was added thereto at 5 DEG C or lower And the mixture was stirred at room temperature for 2 hours. Then, 40.0 g of ice water was slowly added thereto and stirred for 30 minutes. The collected organic layer was concentrated under reduced pressure, and the obtained solid was purified through column chromatography (developing solvent ethyl acetate / n-hexane = 1/8) to obtain a brown solid compound 8 ) (Yield: 81.5%).

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

MS (m / e): 318

Synthesis 4-2) Synthesis of 1- (9,9-dimethyl-9H-fluoren-2-yl) -3-cyclopentyl-1,2-propanedione-

5.0 g of the compound (8) synthesized in Synthesis 4-1 was dissolved in 50 ml of tetrahydrofuran, 0.2 g of isoamyl nitrate and 25 ml of hydrochloric acid gas were added, and the mixture was stirred at 5 캜 for 6 hours. After completion of the reaction, 50 mL of diethyl ether and 50 mL of distilled water were added. The mixture was stirred at room temperature for 10 minutes, and the collected organic layer was concentrated under reduced pressure. The resulting liquid was purified through column chromatography (developing solvent ethyl acetate / n-hexane = 1/8) (Yield: 50.8%) of white solid compound (9).

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

MS (m / e): 347

Synthesis 4-3) Synthesis of Compound 4

2.5 g of the compound (9) synthesized in Synthesis 4-2 was dissolved in 25.0 g of MC, 0.8 g of acetyl chloride was added at 5 캜 or lower, 1.2 g of triethylamine was added dropwise at the same temperature, and the mixture was stirred for 3 hours. When the reaction was completed, 50 mL of distilled water was added and stirred for 10 minutes. The recovered organic layer was concentrated under reduced pressure, and the resulting yellow liquid was purified through column chromatography (developing solvent ethyl acetate / n-hexane = 1/8) Yield: 86.2%).

¹ H NMR (? Ppm; CDCl ₃ ): 1.67-1.92 (m, 15H), 2.04 (d,

MS (m / e): 389

[Example 5] 1- (9,9-dipropyl-9 H -Fluoren-2-yl) -3-cyclopentyl-1,2-propanedione-2-oxime- O -Acetate Compound 5 < RTI ID = 0.0 >

Synthesis 5-1) 1- (9,9-Dipropyl-9 H -Fluoren-2-yl) -3-cyclopentyl-1-propanone (15)

10.0 g of the compound (1) synthesized in Synthesis 1-1 was dissolved in 80 mL of dichloromethane, cooled to 5 캜 or lower, and then added with 9.0 g of aluminum chloride. Then, 5.8 g of n-octanoyl chloride was added dropwise at 5 캜 or lower The mixture was stirred at room temperature for 2 hours. Then, 80.0 g of ice water was slowly added thereto, stirred for 30 minutes, and the recovered organic layer was concentrated under reduced pressure. The obtained solid was purified through column chromatography (developing solvent ethyl acetate / n-hexane = 1/8) to obtain reddish brown compound (10) 11.6 g (yield: 77.2%) was obtained.

^{1 H NMR (δ ppm; CDCl} 3): 0.91 (m, 6H), 1.31 ~ 1.42 (m, 7H), 1.64 ~ 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-fluoren-2-yl) -3-cyclopentyl-1,2-propanedione-

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

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

MS (m / e): 403

Synthesis 5-3) Synthesis of Compound 5

5.0 g of the compound (11) synthesized in Synthesis 5-2 was dissolved in 50.0 g of MC, and 1.3 g of acetyl chloride was added thereto at 5 캜 or lower. 2.0 g of triethylamine was added dropwise thereto at the same temperature, followed by stirring for 3 hours. When the reaction was completed, 100 mL of distilled water was added and stirred for 10 minutes. The recovered organic layer was concentrated under reduced pressure, and the resulting yellow liquid was purified through column chromatography (eluent ethyl acetate / n-hexane = 1/8) to obtain 4.7 g (Yield: 85.9%).

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

MS (m / e): 445

[Example 6] 1- (9,9-Dipropyl-9 H -Fluoren-2-yl) -3-cyclopentyl-1,2-propanedione-2-oxime- O -Benzoate Compound 6 < RTI ID = 0.0 >

Synthesis 6-1) Synthesis of Compound 6

5.0 g of the compound (11) synthesized in Synthesis 5-2 was dissolved in 50.0 g of MC, 2.3 g of benzoyl chloride was added at 5 deg. C or lower, 2.0 g of triethylamine was added dropwise at the same temperature, and the mixture was stirred for 3 hours. After the reaction was completed, 100 mL of distilled water was added and the mixture was stirred for 10 minutes. The recovered organic layer was concentrated under reduced pressure, and the resulting yellow liquid was purified by column chromatography (eluent ethyl acetate / n-hexane = 1/8) to obtain 5.6 g Yield: 89.4%).

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

MS (m / e): 507

[Example 7] Synthesis of 1- (9,9-dipropyl-9 H -Fluoren-2-yl) -4-cyclopentyl-1,2-butanedione-2-oxime- O -Acetate Compound 7 < RTI ID = 0.0 >

Synthesis 7-1) 1- (9,9-Dipropyl-9 H -Fluoren-2-yl) -4-cyclopentyl-1-butanone (12)

5.0 g of the compound (1) synthesized in Synthesis 1-1 was dissolved in 40 ml of dichloromethane, cooled to 5 占 폚 or lower, and 4.5 g of aluminum chloride was added thereto. 3.2 g of n-octanoyl chloride was added dropwise at 5 占 폚 or lower The mixture was stirred at room temperature for 2 hours. Then, 40.0 g of ice water was slowly added thereto and stirred for 30 minutes. The collected organic layer was concentrated under reduced pressure, and the obtained solid was purified through column chromatography (eluent ethyl acetate / n-hexane = 1/8) to obtain reddish brown compound (12) 6.3 g (yield: 80.8%) was obtained.

^{1 H NMR (δ ppm; CDCl} 3): 0.91 (m, 6H), 1.21 ~ 1.44 (m, 9H), 1.71 ~ 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-fluoren-2-yl) -4-cyclopentyl-1,2-butanedione-

5.0 g of the compound (12) synthesized in Synthesis 7-1 was dissolved in 50 ml of tetrahydrofuran, 0.2 g of isoamyl nitrate and 47 ml of hydrochloric acid gas were added, and the mixture was stirred at 10 캜 for 6 hours. After completion of the reaction, 50 mL of diethyl ether and 10 mL of distilled water were added. The mixture was stirred at room temperature for 10 minutes, and the collected organic layer was concentrated under reduced pressure. The obtained liquid was purified through column chromatography (eluent ethyl acetate / n-hexane = 1/8) 3.3 g (yield: 61.7%) of a brown solid compound (13) was obtained.

^{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 ~ 8.12 (m, 7H ), 11.0 (s, 1 H)

MS (m / e): 417

Synthesis 7-3) Synthesis of Compound 7

3.0 g of the compound (13) synthesized in Synthesis 7-2 was dissolved in 30.0 g of MC, 0.8 g of acetyl chloride was added at 5 캜 or lower, 1.2 g of triethylamine was added dropwise at the same temperature, and the mixture was stirred for 3 hours. After the reaction was completed, 30 mL of distilled water was added and stirred for 10 minutes. The recovered organic layer was concentrated under reduced pressure, and the resulting yellow liquid was purified through column chromatography (developing solvent ethyl acetate / n-hexane = 1/8) to obtain 2.8 g (Yield: 84.2%).

¹ H NMR (? Ppm; CDCl ₃ ): 0.90 (m, 6H), 1.31-1.44 (m, 7H), 1.65-1.92 7.25 ~ 8.12 (m, 7H),

MS (m / e): 459

[Comparative Example 1] Synthesis of Compound 8

Using the precursor obtained by reacting n-propylbromide with Fluorene by applying the method described in Example 1, the following compound 8 was synthesized.

 Compound 8 (Comparative Example 1)

[Comparative Example 2] Compound 9

The commercially available OXE-01 was used as Comparative Example 2.

Compound 9 (Comparative Example 2)

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

Experimental Example 1: Evaluation of pyrolysis temperature

Pyrolysis temperature was measured using PerkinElmer TGA (Pyris 1) (10 ° C / 10 min, N ₂ ).

Experimental Example 2: Evaluation of maximum absorption wavelength and Gram absorption coefficient

Shimadzu UV-3600 UV-VIS-NIR spectrophotometer at a concentration of 20 ppm in Acetonitrile.

Experimental Example 3: Evaluation of solubility

And the degree of dissolution in 20 g of PGMEA at 20 캜 was evaluated.

From the above results, it can be seen that the compounds of Examples are superior in thermal stability to those of Compound 8 (Comparative Example 1) and OXE-01 (Comparative Example 2) . In addition, the solubility is excellent and the Gram absorption coefficient at the maximum absorption wavelength is high, which indicates that the characteristics are superior to those of the conventional photoinitiator.

[Production Example 1] Production of blue negative photosensitive resin composition using Examples 1 to 7

≪ Preparation of blue dispersion (A) >

After mixing 80 g of solvent propylene glycol monomethyl ether acetate (PGMEA), 12 g of blue pigment Pigment Blue 15: 6, 4 g of dispersant (Disperbyk-163 manufactured by BYK Corp.) and 4 g of alkali soluble resin (acrylate system) After stirring for 2 hours using a stirrer, 0.3 mm zirconia beads were charged, and the mixture was stirred at a speed of 8 m / s using a bead mill manufactured by Netscreen for 3 hours to obtain a blue pigment dispersion (A).

≪ Preparation of alkali 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 P GMEA were added to the reaction vessel and stirred at 120 캜 for 22 hours while air bubbling was performed. Thereafter, the reaction solution was cooled to 90 占 폚, and 60 g of bisphenol anhydride was added, followed by stirring at 120 占 폚 for 8 hours. After cooling to 90 ° C, 20 g of tetrahydrophthalic anhydride and 100 g of PGAMEA were added and further stirred at 120 ° C for 6 hours. Thereafter, the mixture was cooled to room temperature to obtain an alkali developable resin (B). At that time, the solid content was 50%, Mn = 3500 and acid value (solid content) was 95.3 mg KOH / g.

≪ Preparation of alkali developable resin (C) >

84.5 g of cinnamyl alcohol, 76.6 g of triethylamine, 0.14 g of polymerization inhibitor and 422 g of dichloromethane as a solvent were added to the reaction vessel, and 106.7 g of methacrylate was slowly added thereto while maintaining the temperature at room temperature. After the addition was completed, the temperature was raised to 40 ° C and maintained for 24 hours. Water was then added to conduct extraction and concentration to obtain cinnamic methacrylate. (C) was obtained by charging 96.8 g of cinnamyl methacrylate, 33.3 g of methacrylic acid, 12 g of styrene, 11.0 g of AIBN and 230 g of PGMEA and holding at 85 캜 for 6 hours. At this time, the solid content was 40%, Mn was 8,800 and acid value (solid content) was 160 mg KOH / g.

≪ Preparation of blue photosensitive resin composition >

6.8 g of the alkali developable resin (B), 2.8 g of the alkali developable resin (C), 0.6 g of dipentaerythritol penta and hexaacrylate, 1.5 g of photopolymerization initiators (compounds 1 to 7) 0.05 g of an activator was added and stirred, and PGMEA was added so that the final solid concentration was 20% by weight to obtain a blue negative photosensitive resin composition.

[Preparation Example 2] Preparation of blue negative photosensitive resin composition using a comparative compound

A blue negative photosensitive resin composition was prepared in the same manner as in Production Example 1 except that the photopolymerization initiator was used instead of the compound 1 to 7 (Comparative Example 1) and Compound 9 (Comparative Example 2) .

Comparative Example 1 Comparative Example 2

[Experimental Example 4] Evaluation of required minimum exposure dose, line width, luminance, adhesion

The photosensitive resin composition prepared in Preparation Example 1 and Preparation Example 2 was coated on a substrate, and the lowest exposure dose, line width, luminance and adhesion were evaluated.

[Minimum light exposure required]

The minimum exposure dose at which the film thickness after development became 80% or more of the film thickness of the coated film after coating was regarded as the minimum exposure dose, and the sensitivity was evaluated.

[Line width]

Means the width of the pattern generated when the same 60 mJ / cm ² is exposed and developed, and the higher the line width, the higher the sensitivity.

[Brightness]

After the development, measurements were made using a color difference meter (CA-310, Konica Minolta).

[Adhesion (resolution)]

After the exposure and development were performed at the same 60 mJ / cm ² , the smallest mask line width of the remaining pattern was measured. ? When the thickness is 10 占 퐉 or less,? When the thickness is 15 占 퐉 or less, and X when the thickness is 20 占 퐉 or less.

According to Table 4, the blue negative photosensitive resin compositions prepared according to Preparation Example 1 including the compounds of Examples 1 to 7 have excellent physical properties such as high sensitivity and excellent adhesiveness.

[Production Example 3] Preparation of black negative photosensitive resin composition (for black matrix)

19.8 g of the alkali developable resin (B), 5 g of dipentaerythritol penta and hexaacrylate, 1.0 g of the compounds of the compounds 1 to 7 as photopolymerization initiators, and 0.05 g of a surfactant 0.05 were added to 45 g of a solution of carbon black dispersion (solid content 22% in PGMEA) g, and stirred. PGMEA was added so that the final solid concentration became 20% by weight to obtain a black negative photosensitive resin composition.

[Preparation Example 4] Preparation of black negative photosensitive resin composition using a comparative compound

A black negative photosensitive resin composition was prepared in the same manner as in Production Example 3 except that Comparative Example Compound 8-9 was used as a photopolymerization initiator instead of Compound 1-7.

[Experimental Example 5] Evaluation of Line Width, Adhesion and Developability

The black negative photosensitive resin compositions prepared in Preparative Examples 3 and 4 were coated on a substrate, and the minimum exposure amount, line width, brightness, and adhesion were evaluated.

[Line width]

Means the width of the pattern generated when the same 40 mJ / cm ² is exposed and developed, and the higher the line width, the higher the sensitivity.

[Adhesion (resolution)]

After the same 40 mJ / cm ² exposure and development for the same time (33 seconds), the smallest mask line width of the remaining pattern was measured. ? When the thickness is 10 占 퐉 or less,? When the thickness is 15 占 퐉 or less, and X when the thickness is 20 占 퐉 or less.

[Developability]

It was confirmed by the time (seconds; break point) at which the dissolution started at the time of development. Developability is better as the breakpoint is shorter.

According to Table 5, it can be seen that the black negative photosensitive resin composition comprising the photoinitiators of Examples 1 to 7 according to the present invention has excellent physical properties such as excellent adhesiveness and developability.

[Production Example 5] Production of transparent negative photosensitive resin composition using the compounds 1 to 7 (for an insulating film)

41 g of dipentaerythritol penta and hexaacrylate, 2.0 g of photopolymerization initiator compounds 1 to 7 and 0.2 g of a surfactant were added to 12.0 g of the alkali developable resin (B) and 24.0 g of the alkali developable resin (C) PGMEA was added so that the final solid concentration was 20% by weight to obtain a transparent negative photosensitive resin composition.

[Production Example 6] Production of transparent negative photosensitive resin composition using Comparative Examples 8 and 9 (for insulating film)

A transparent negative photosensitive resin composition was prepared in the same manner as in Production Example 5 except that the compounds of Comparative Examples 8 and 9 (Comparative Examples 1 and 2) were used as a photopolymerization initiator instead of the compounds of Examples 1 to 7.

[Experimental Example 6] Evaluation of residual film ratio and resolving power

The film thickness of the film formed by coating the transparent negative photosensitive resin composition prepared in Production Example 5 and Production Example 6 on the substrate and then exposed to light was evaluated.

[Remaining film ratio]

The ratio of the film thickness before exposure, the exposure, and the film thickness after development is defined as the retention rate. The higher the residual film ratio, the higher the sensitivity.

[definition]

The minimum pattern size was defined as the resolution after exposure and development of the same 60 mJ / cm ² .

According to Table 6, the transparent negative photosensitive resin compositions containing the photoinitiators of the compounds 1 to 7 prepared according to Production Example 5 have excellent physical properties such as excellent resolution and developability.

Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (7)

An oxime ester compound represented by the following Formula 1:
[Chemical Formula 1]

In this formula,
R ₁ is a methyl or phenyl group,
R ₂ and R ₃ are each selected from hydrogen, a methyl group, an ethyl group, a propyl group and a butyl group,
n is an integer of 1 to 4,
m is an integer of 0 to 6,
Provided that when n is 1, m is an integer of 1 to 6;
A photopolymerization initiator comprising the oxime ester compound according to claim 1 as an active ingredient.
A photosensitive resin composition comprising the photopolymerization initiator of claim 2, a compound having an ethylenically unsaturated bond, and a binder resin.
The method of claim 3,
Wherein the photosensitive resin composition is a negative type photosensitive resin composition used for the production of a color filter, a black matrix, an organic insulating film, a column spacer, or an overcoat.
The method of claim 3,
Wherein the photosensitive resin composition comprises 0.01 to 10% by weight of an oxime ester compound of Formula 1, 0.001 to 50% by weight of a polymerizable compound having an ethylenically unsaturated bond, 10 to 95% by weight of a solvent and 5 to 60% Wherein the photosensitive resin composition is a photosensitive resin composition.
The method of claim 4, wherein
Wherein the photosensitive resin composition is for a black mattress further comprising carbon black.
The method of claim 4, wherein
Wherein the photosensitive resin composition is for a color matrix further comprising a coloring material.