1. A black photosensitive resin composition comprising a black colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an epoxy compound and a compound having a thiol group,

the photopolymerizable compound contains a photopolymerizable compound having 4 or less functional groups.

2. The black photosensitive resin composition according to claim 1, wherein the photopolymerizable compound comprises a hydroxyl group-containing photopolymerizable compound having a functionality of 4 or less.

3. The black photosensitive resin composition according to claim 1, wherein the 4-or lower-functional photopolymerizable compound is at least one selected from the group consisting of ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate.

4. The black photosensitive resin composition according to claim 1, wherein the content of the epoxy compound is 1 to 20% by weight based on 100% by weight of the total solid content in the black photosensitive resin composition.

5. The black photosensitive resin composition according to claim 1, wherein the content of the compound having a thiol group is 0.1 to 4% by weight based on 100% by weight of the total solid content in the black photosensitive resin composition.

6. The black photosensitive resin composition according to claim 1, which is used for a flexible substrate.

7. A black matrix formed using the black photosensitive resin composition according to any one of claims 1 to 6.

8. An image display device comprising the black matrix of claim 7.

Background

The black photosensitive resin composition is an essential material for color filters, liquid crystal display devices, organic light-emitting elements, displays, and the like. For example, in a color filter of a color liquid crystal display, a light shielding layer is formed at a boundary portion between coloring layers such as red (red), green (green), and blue (blue), whereby display contrast and a color development effect can be improved.

Specifically, in pixels formed of red (R), green (G), and blue (B) colors, a black matrix is formed at the boundary between the colored layers of each pixel, or a columnar spacer is formed at the portion in contact with the liquid crystal, in order to prevent color mixing with other colors or to hide the electrode pattern.

In recent years, attention has been paid to development of a flexible display device that can be rolled or folded like paper. Accordingly, materials that can be used for various substrates used in display devices are limited to flexible polymer materials because they are required to have flexible characteristics. Further, due to such material limitations, the manufacturing process is also required to be performed under more mild conditions.

Therefore, the necessity for changing the curing conditions of the photosensitive resin composition from the conventional high-temperature curing to the low-temperature curing is also remarkable. However, low-temperature curing has a problem that reactivity is lowered and durability of a formed pattern is lowered.

Korean patent laid-open publication No. 2015-0062889 discloses that a photosensitive resin composition for black columnar spacers, which includes an alkali-soluble binder resin, a polyfunctional monomer, a colorant, a solvent, and an oxime-based photoinitiator having long-wavelength band absorbability, is excellent in process characteristics and post-baking characteristics.

However, the photosensitive resin composition has a problem that it is difficult to secure sufficient durability at the time of curing at low temperature. Therefore, development of a black photosensitive resin composition having excellent low-temperature curability and excellent solvent resistance and adhesion during low-temperature curing has been demanded so as to be applicable to a flexible substrate made of a polymer material.

Further, since it is difficult to expect that the reverse slope forms a positive slope by reflow (reflow) at the time of low-temperature curing, it is necessary to develop a black photosensitive resin composition that exhibits a positive taper angle also at the time of low-temperature curing.

Disclosure of Invention

Problems to be solved

An object of the present invention is to provide a low-temperature curable black photosensitive resin composition which exhibits a positive taper angle and is excellent in solvent resistance and adhesion.

Another object of the present invention is to provide a black matrix formed by using the black photosensitive resin composition.

Still another object of the present invention is to provide an image display device including the black matrix.

Means for solving the problems

In one aspect, the present invention provides a black photosensitive resin composition comprising a black colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an epoxy compound, and a compound having a thiol group, wherein the photopolymerizable compound comprises a photopolymerizable compound having a functionality of 4 or less.

In one embodiment of the present invention, the photopolymerizable compound may include a photopolymerizable compound having a hydroxyl group and a functionality of 4 or less.

In one embodiment of the present invention, the 4-or lower-functional photopolymerizable compound may be at least one selected from the group consisting of ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate.

In one embodiment of the present invention, the content of the epoxy compound may be 1 to 15% by weight based on 100% by weight of the total solid content in the black photosensitive resin composition.

In one embodiment of the present invention, the content of the compound having a thiol group may be 0.1 to 4% by weight based on 100% by weight of the total solid content in the black photosensitive resin composition.

The black photosensitive resin composition according to one embodiment of the present invention can be used for a flexible substrate.

In another aspect, the present invention provides a black matrix formed using the black photosensitive resin composition.

In still another aspect, the present invention provides an image display device including the black matrix.

Effects of the invention

The black photosensitive resin composition of the present invention exhibits a positive taper angle even when cured at low temperatures, and is excellent in solvent resistance and adhesion. Therefore, the black photosensitive resin composition of the present invention can improve the reverse taper angle of a pattern and can form a pattern having excellent durability even when applied to a flexible substrate made of a polymer material.

Detailed Description

The present invention will be described in more detail below.

One embodiment of the present invention relates to a black photosensitive resin composition comprising a black colorant (a), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), an epoxy compound (E), and a compound (F) having a thiol group, wherein the photopolymerizable compound (C) comprises a photopolymerizable compound having a functionality of 4 or less.

Black colorant (A)

In one embodiment of the present invention, the black colorant (a) is used for black color, and light-shielding properties are provided to the spacers, the black matrix, and the black columnar spacers. The black column spacer means that the column spacer is integrally formed with the black matrix. That is, the black matrix can prevent light leakage, and the spacer can prevent malfunction of the device due to light from the outside.

As the black colorant, any black colorant known in the art, such as an organic pigment, a dye, and an inorganic pigment, may be used as long as it has a light-shielding property in visible light, and a black pigment containing an organic pigment and/or an inorganic pigment is preferably used.

As the black pigment, known black pigments can be used without particular limitation, and specifically, lactam black, aniline black, perylene black, titanium black, carbon black, and the like can be used. These may be used singly or in combination. Examples of the carbon black include channel black, furnace black, thermal black, and lamp black.

If necessary, carbon black coated with a resin on the surface may be used for electrical insulation. This is because the resin-coated carbon black has lower electrical conductivity than the resin-uncoated carbon black, and therefore can provide excellent electrical insulation properties when forming a black matrix, a spacer, or a black columnar spacer (black matrix-integrated spacer).

Further, the black colorant may optionally further contain a color correction agent. As the color correcting agent, violet (violet) pigment, blue (blue) pigment, yellow (yellow) pigment, green (green) pigment, and the like can be used, and specifically, condensed polycyclic pigments such as anthraquinone-based pigment and perylene-based pigment, organic pigments such as phthalocyanine pigment and azo pigment, and the like can be used, and anthraquinone-based pigment or phthalocyanine pigment is preferable, and phthalocyanine pigment is more preferable. Examples of the phthalocyanine pigment include c.i. pigment blue 15:6, c.i. pigment blue 15:4, and c.i. pigment blue 16, and examples of the anthraquinone-based pigment include c.i. pigment blue 60. The phthalocyanine pigment may preferably be c.i. pigment blue 15: 6.

The black colorant may include one or more black organic pigments selected from the group consisting of lactam black, aniline black, and perylene black; and one or more black inorganic pigments selected from the group consisting of titanium black and carbon black.

Among the black organic pigments, lactam black (e.g., from Pasteur corporation) is preferably used in view of optical density, dielectric constant, and transmittanceBlack S 0100CF)。

Among the black inorganic pigments, carbon black is preferably used from the viewpoint of pattern characteristics and chemical resistance.

The content of the black colorant (a) may be 20 to 80% by weight, preferably 20 to 70% by weight, based on 100% by weight of the total solid content in the black photosensitive resin composition. In the case where the content of the black colorant is within the above range, the optical density may become excellent.

In the present invention, the solid content in the black photosensitive resin composition means the total amount of components obtained by removing the solvent.

The pigment is preferably a pigment dispersion liquid in which the particle size of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method in which a pigment dispersant (a1) is added to the dispersion medium and the dispersion is performed, and according to the above method, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.

Pigment dispersant (a1)

The pigment dispersant (a1) is added for the purpose of disaggregation of the pigment and maintaining stability, and any pigment dispersant generally used in the art can be used without limitation. Commercially available dispersants include LPN-6919, Disperbyk-101, 103, 107, 108, 110, 111, 112, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, etc. of Bikk (BYK), SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 20700, 27000, 3100, 31845, 32000, 280500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53000, 76500, etc.

These may be used alone or in combination of two or more. Preferably, the pigment dispersant includes, but is not limited to, LPN-6919 from Pico, Disperbyk-2000, 2001 from Pico as a dispersant having an acidic functional group, and SOLSPERSE-3000, 21000, 26000, 36600, 41000 from Loborun.

The content of the pigment dispersant (a1) may be 5 to 60 parts by weight, and more preferably 15 to 50 parts by weight, based on 100 parts by weight of the pigment. If the content of the pigment dispersant is more than 60 parts by weight, the viscosity may be increased, and if it is less than 5 parts by weight, problems such as difficulty in microparticulation of the pigment or gelation after dispersion may be caused.

Alkali soluble resin (B)

In one embodiment of the present invention, the alkali-soluble resin (B) has reactivity and alkali solubility by the action of light or heat, and any resin known in the art can be selected and used without any particular limitation as long as it functions as a dispersion medium for solid components such as a colorant and functions as a binder resin.

Specifically, the alkali-soluble resin is preferably a copolymer of an unsaturated carboxyl group-containing monomer and another monomer copolymerizable therewith.

Examples of the unsaturated carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated polycarboxylic acids having 2 or more carboxyl groups in the molecule, such as unsaturated tricarboxylic acids.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, and carnosic acid.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the above-mentioned unsaturated polycarboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, and for example, may be mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate or the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends thereof, and examples thereof include ω -carboxy polycaprolactone monoacrylate, ω -carboxy polycaprolactone monomethacrylate and the like.

The carboxyl group-containing monomers may be used alone or in combination of two or more.

Examples of the other monomer copolymerizable with the above carboxyl group-containing monomer include 3, 4-epoxytricyclo [5 ].2.1.0^2,6]Decane-9-yl acrylate, 3, 4-epoxytricyclo [5.2.1.0^2,6](meth) acrylic acid epoxy ester compounds such as decane-8-yl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether and the like; aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, indene and the like; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, n-butyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-butyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, 2-butyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-butyl acrylate, 2-hydroxy-butyl acrylate, 2-hydroxy-butyl acrylate, 2-hydroxy-butyl acrylate, and 2-butyl acrylate, 2-hydroxy-butyl acrylate, 2-hydroxy-butyl acrylate, 2-butyl acrylate, and, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol diacrylate, allyl methacrylate, benzyl acrylate, cyclohexyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy propylene glycol acrylate, methoxy propylene, Methoxy dipropylene glycol methacrylate, isobornyl acrylate and methacrylic acid isoacrylateUnsaturated carboxylic acid esters such as bornyl ester, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; aminoalkyl esters of unsaturated carboxylic acids such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; and macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, and the like. These monomers may be used each alone or in combination of two or more.

In the present specification, "(meth) acrylate" is a term including acrylate and/or methacrylate.

The acid value of the alkali-soluble resin (B) may be 10 to 100KOH mg/g. If the acid value is within the above range, the solubility in the developer is increased, the non-exposed portion is easily dissolved, the sensitivity is increased, and as a result, the pattern of the exposed portion is left during development to improve the film remaining ratio (film remaining ratio), which is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the polymer, and can be usually determined by titration with an aqueous potassium hydroxide solution.

The alkali-soluble resin (B) may have a polystyrene-equivalent weight average molecular weight (hereinafter, simply referred to as "weight average molecular weight") of 3,000 to 200,000, preferably 5,000 to 100,000, as measured by gel permeation chromatography (GPC; with tetrahydrofuran as an eluting solvent). When the molecular weight is within the above range, the hardness of the coating film tends to be increased, the film retention rate tends to be high, the solubility of the unexposed area in the developer tends to be excellent, and the resolution tends to be improved.

The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the alkali-soluble resin (B) may be 1.5 to 6.0, and preferably 1.8 to 4.0. It is preferable that the molecular weight distribution is in the above range because the developability is excellent.

The content of the alkali-soluble resin (B) may be 1 to 30% by weight, preferably 5 to 20% by weight, based on 100% by weight of the total solid content in the black photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, a black photosensitive resin composition having excellent developability and a cured film having excellent chemical resistance can be easily obtained.

Photopolymerizable compound (C)

In one embodiment of the present invention, the photopolymerizable compound (C) is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and is polymerized by an exposure process to improve the mechanical properties of a colored pattern or enhance the developability of the alkali-soluble resin.

The photopolymerizable compound contains a photopolymerizable compound having 4 or less functional groups. The photosensitive resin composition of the present invention contains a photopolymerizable compound having a functionality of 4 or less, so that a positive slope having a pattern taper angle of 90 degrees or less can be formed before the post-baking step. In the case of a low-temperature curable composition in which the post-baking step is performed at 100 ℃ or lower, it is difficult to expect that the reverse slope becomes a positive slope by reflow (reflow) in the post-baking process, and therefore it is very important to form a positive slope before the post-baking step. In addition, the photosensitive resin composition of the present invention contains a photopolymerizable compound having a functional group of 4 or less, and thus has excellent adhesion to the lower substrate and facilitates formation of a fine pattern.

In particular, when the photopolymerizable compound contains a 4-functional or lower photopolymerizable compound having a hydroxyl group, it is preferable from the viewpoint of the normal slant and the improvement of the adhesion force.

Examples of the 4-or lower-functional photopolymerizable compound include monofunctional monomers such as nonylphenylcarbinol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and N-vinylpyrrolidone; difunctional monomers such as 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, and 3-methylpentanediol di (meth) acrylate; and polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. They may be used alone or in combination of two or more.

In particular, as the 4-or lower-functional photopolymerizable compound, one or more selected from the group consisting of ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate may be used.

The photopolymerizable compound may further contain a photopolymerizable compound having more than 4 functions and not more than 8 functions within a range not to impair the effects of the present invention.

Examples of the photopolymerizable compound having more than 4 functions and not more than 8 functions include dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. They may be used alone or in combination of two or more.

Preferably, the content of the photopolymerizable compound having more than 4 functions and not more than 8 functions may be less than 30% by weight based on 100% by weight of the total photopolymerizable compound. If the content of the photopolymerizable compound having more than 4 functions and not more than 8 functions is 30 wt% or more, it is difficult to expect that the pattern will be a positive slope and the adhesion to the lower substrate may be reduced.

The content of the photopolymerizable compound (C) may be 1 to 40% by weight, preferably 10 to 30% by weight, based on 100% by weight of the total solid content in the black photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, it is preferable from the viewpoint of the intensity and smoothness of the pixel portion.

Photopolymerization initiator (D)

In one embodiment of the present invention, the photopolymerization initiator (D) may be used without particular limitation as long as it can polymerize the photopolymerizable compound (C). In particular, from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like, it is preferable to use one or more compounds selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, oxime compounds, and thioxanthone compounds as the photopolymerization initiator (D).

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, and mixtures thereof, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

Examples of the benzophenone-based compound include benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone.

Specific examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethylene ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [2- (furan-2- Yl) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) ethylene ] -1,3, 5-triazine, and the like.

Specific examples of the biimidazole-based compound include 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) biimidazole, 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetrakis (trialkoxyphenyl) biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, or biimidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted with an alkoxycarbonylyl group, and the like. Among them, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole are preferably used.

Specific examples of the oxime-based compound include o-ethoxycarbonyl- α -oxyimino-1-phenylpropan-1-one, 1, 2-octanedione, -1- (4-phenylthio) phenyl, -2- (o-benzoyloxime), ethanone, -1- (9-ethyl) -6- (2-methylbenzoyl-3-yl) -,1- (o-acetyloxime), and commercially available products include CGI-124 (Ciba Geigy), CGI-224 (Ciba Geigy), Irgacure OXE-01 (Basofv), Irgacure OXE-02 (Basofv), N-1919 (ADEKA), and NCI-831 (ADEKA).

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

Further, other photopolymerization initiators and the like than those described above may be added and used within a range not impairing the effects of the present invention. For example, benzoin-based compounds and anthracene-based compounds may be used, and they may be used alone or in combination of two or more.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the anthracene compound include 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, and 2-ethyl-9, 10-diethoxyanthracene.

In addition, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9, 10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, or the like may be used in combination as a photopolymerization initiator.

The content of the photopolymerization initiator (D) may be 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on 100% by weight of the total solid content in the black photosensitive resin composition. The content range is preferably used in the above range, because the photopolymerization rate of the photopolymerizable compound and the physical properties of the finally obtained coating film are taken into consideration, and if the content is less than the above range, the polymerization rate is low and the overall process time may be long, whereas if the content is more than the above range, the crosslinking reaction may be lost due to excessive reaction and the physical properties of the coating film may be rather deteriorated.

Further, a photopolymerization initiation aid may be used together with a photopolymerization initiator, and when the photopolymerization initiation aid is used together with the photopolymerization initiator, the black photosensitive resin composition is more highly sensitive and productivity is improved, which is preferable. As the photopolymerization initiation aid, one or more compounds selected from the group consisting of amine compounds and carboxylic acid compounds can be preferably used.

Such a photopolymerization initiator aid is preferably used in an amount of usually 10 moles or less, preferably 0.01 to 5 moles per 1 mole of the photopolymerization initiator. When the photopolymerization initiator is used in the above range, the polymerization efficiency can be improved, and the effect of improving productivity can be expected.

Epoxy Compound (E)

In one embodiment of the present invention, the epoxy compound (E) is a compound having an epoxy group in a molecule as a component which improves the curing degree.

For example, as the epoxy compound (E), an alicyclic epoxy compound, a bisphenol a type epoxy compound, a bisphenol F type epoxy compound, a novolak type epoxy compound, a polyfunctional amine epoxy compound, and the like can be used, and these can be used alone or in combination of two or more. As the epoxy compound (E), an alicyclic epoxy compound, particularly a 2-functional alicyclic epoxy compound is preferably used in view of low-temperature curability and solvent resistance.

Specifically, as the alicyclic epoxy compound, one or more compounds represented by the following chemical formulas 2 to 3 can be used.

[ chemical formula 2]

[ chemical formula 3]

In the above-mentioned formula, the compound of formula,

n is an integer of 0 or 1.

In one embodiment of the present invention, the content of the epoxy compound may be 1 to 20% by weight, preferably 5 to 15% by weight, based on 100% by weight of the total solid content in the black photosensitive resin composition. If the content of the above epoxy compound is less than 1% by weight relative to 100% by weight of the total solid content in the black photosensitive resin composition, it may be difficult to obtain a good cured film at low temperature, and if the content is more than 20% by weight, the surface flatness may be reduced.

Compound having thiol group (F)

In one embodiment of the present invention, the compound (F) having a thiol group is a compound having 1 or more thiol groups in a molecule as a component which improves the low-temperature heat curing degree. When the compound having a thiol group is used together with the epoxy compound, the thermal reaction temperature can be lowered to improve the low-temperature curability.

For example, the compound having a thiol group may be a compound represented by the following chemical formula 1, but is not limited thereto.

[ chemical formula 1]

In the above-mentioned formula, the compound of formula,

L¹is carbon, substituted or unsubstituted alkylene of C2-C20, substituted or unsubstituted heteroalkylene of C2-C20, substituted or unsubstituted arylene of C6-C30, substituted or unsubstituted heteroarylene of C3-C30, substituted or unsubstituted cycloalkylene of C3-C30, or substituted or unsubstituted heterocycloalkylene of C3-C30,

Y^a～Y^deach independently is absent; or substituted or unsubstituted alkylene of C1-C30, substituted or unsubstituted alkenylene of C2-C30; or at least one methylene group (-CH)₂-) by sulfonyl (-S (═ O)₂-), a carbonyl group (-O) -), an ether group (-O-), a thioether group (-S-), a sulfoxide group (-S (-O) -), an ester group (-C (-O) O-), an amide group (-C (-O) NR-) (wherein R is hydrogen or a linear or branched alkyl group of C1-C10), a sulfoxide group (-O-), and a sulfide group (-S-)Amino (-NR-) (wherein R is hydrogen or C1-C10 linear or branched alkyl) or their combination substituted C1-C30 alkylene or C2-C30 alkenylene,

R^a～R^deach independently hydrogen, substituted or unsubstituted C1-C30 straight chain or branched chain alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, C1-C10 alkoxy, hydroxyl, -NH₂Substituted OR unsubstituted amine group (-NRR ', wherein R and R' are each independently hydrogen OR a linear OR branched alkyl group of C1 to C30), isocyanate group, halogen, -ROR '(wherein R is a substituted OR unsubstituted alkylene group of C1 to C20 and R' is hydrogen OR a linear OR branched alkyl group of C1 to C4934), acid halide (-RC (═ O) X, wherein R is a substituted OR unsubstituted alkylene group and X is halogen), -C (═ O) OR '(wherein R' is hydrogen OR a linear OR branched alkyl group of C1 to C20), -CN, OR-C (═ O) ONRR '(wherein R and R' are each independently hydrogen OR a linear OR branched alkyl group of C1 to C20), OR SH, R^a～R^dAt least 1 of which is SH,

p and q are each independently an integer of 1 to 2.

Hereinafter, unless otherwise specified, the term "substituted" means that hydrogen in a compound is substituted by a group selected from the group consisting of C1-C30 alkyl, C2-C30 alkynyl, C6-C30 aryl, C7-C30 alkylaryl, C1-C30 alkoxy, C1-C30 heteroalkyl, C3-C30 heteroalkylaryl, C3-C30 cycloalkyl, C3-C15 cycloalkenyl, C6-C30 cycloalkynyl, C2-C30 heterocycloalkyl, halogen (-F, -Cl, -Br or-I), hydroxy (-OH), nitro (-NO)₂) Cyano (-CN), amino (-NRR 'wherein R and R' are independently of each other hydrogen or C1-C6 alkyl), azido (-N)₃) Amidino (-C (═ NH)₂) Hydrazino (-NHNH)₂) Hydrazinyl (═ N (NH)₂) Aldehyde group (-C (═ O) H), carbamoyl group (carbamoyl group, -C (O) NH)₂) Thiol (-SH), ester (-C (═ O) OR, wherein R is C1-C6 alkyl OR C6-C12 aryl), carboxyl (-COOH) OR its salt (-C (═ O) OM, wherein M is organic OR inorganic cationIons), sulfonic acid groups (-SO)₃H) Or a salt thereof (-SO)₃M, wherein M is an organic or inorganic cation), a phosphate group (-PO)₃H₂) Or a salt thereof (-PO)₃MH or-PO₃M₂Wherein M is an organic or inorganic cation) and combinations thereof.

In addition, unless otherwise defined below, the term "hetero" means that 1 to 3 hetero atoms selected from N, O, S, Si and P are contained.

In the present specification, the "alkylene group" is a linear or branched saturated aliphatic hydrocarbon group having a valence (value) of 2 or more.

In the present specification, the term "heteroalkylene" refers to a straight or branched chain saturated aliphatic hydrocarbon group having a valence (value) of 2 or more and having one or more chain carbons substituted with a heteroatom.

In the present specification, "arylene" means a functional group having a valence of 2 or more formed by removing at least 2 hydrogens from one or more aromatic rings.

In the present specification, the term "heteroarylene group" means a functional group having a valence of 2 or more and having one or more ring carbons substituted with a hetero atom, which is formed by removing at least 2 hydrogens from one or more aromatic rings.

In the present specification, "cycloalkylene" means a functional group having a valence of 2 or more formed by removing at least 2 hydrogens from one or more saturated aliphatic rings.

In the present specification, "heterocycloalkylene" means a functional group having a valence of 2 or more and having one or more ring carbons substituted with a heteroatom, which is formed by removing at least 2 hydrogens from one or more saturated aliphatic rings.

In the present specification, the "alkenylene group" is a straight-chain or branched unsaturated aliphatic hydrocarbon group having at least one carbon-carbon double bond and having a valence (value) of 2 or more.

In the present specification, an "alkyl group" is a linear or branched saturated aliphatic hydrocarbon group having a valence (value) of 1.

In the present specification, "aryl" means a functional group having a valence of 1 formed by removing 1 hydrogen from one or more aromatic rings.

In the present specification, "heteroaryl" means a functional group having a valence of 1 formed by removing 1 hydrogen from one or more aromatic rings, and having one or more ring carbons substituted with a heteroatom.

In the present specification, "cycloalkyl" means a functional group having a valence of 1 formed by removing 1 hydrogen from one or more saturated aliphatic rings.

In the present specification, "heterocycloalkyl" means a functional group having a valence of 1 formed by removing 1 hydrogen from one or more saturated aliphatic rings, and having one or more ring carbons substituted with a heteroatom.

Specifically, the compound (F) having a thiol group may be 2-ethylhexyl-3-mercaptopropionate, butane-1, 4-diylbis (mercaptoacetate), ethoxylated pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptoacetate), ethylene glycol di- (3-mercaptopropionate), polypropylene glycol 3-mercaptopropionate, ethoxylated trimethylolpropane tris (3-mercaptopropionate), ethylene glycol dimercaptoacetate, ethoxylated ethylene glycol dimercaptoacetate, 1, 4-bis (3-mercaptobutyryloxy) butane, tris [2- (3-mercaptopropionyloxy) ethyl ] isocyanurate, 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (2-mercaptoacetate), dipentaerythritol hexa (3-mercaptopropionate), 1, 6-hexanedithiol, 1, 3-propanedithiol, 1, 2-ethanedithiol, polyethylene glycol dithiol comprising 1 to 10 ethylene glycol repeating units, or a combination thereof.

In one embodiment of the present invention, the content of the compound having a thiol group may be 0.1 to 4% by weight, preferably 1 to 3% by weight, based on 100% by weight of the total solid content in the black photosensitive resin composition. If the content of the compound having a thiol group is less than 0.1% by weight based on 100% by weight of the total solid content in the black photosensitive resin composition, it may be difficult to obtain a good cured film when baking is performed at a low temperature, and if the content is more than 4% by weight, compatibility with a material constituting the photosensitive resin composition may be reduced.

Solvent (G)

The black photosensitive resin composition according to one embodiment of the present invention may further include a solvent (G). The solvent is not particularly limited, and various organic solvents used in the field of photosensitive resin compositions can be used.

Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and 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, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, ketones such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and the like, Alcohols such as glycerol, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ -butyrolactone.

Among the above solvents, from the viewpoint of coatability and drying properties, it is preferable to use an organic solvent having a boiling point of 100 to 200 ℃, more preferably an alkylene glycol alkyl ether acetate, a ketone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate or other ester, and still more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate or other ester. These solvents may be used each alone or in combination of two or more.

The content of the solvent (G) is the balance to make the total weight of the black photosensitive resin composition of one embodiment of the present invention 100 wt%.

Additive (H)

The black photosensitive resin composition according to an embodiment of the present invention may further contain an additive (H) as needed, in addition to the above components.

The additive may further include one or more additives selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-gelling agents.

Specific examples of the other polymer compounds include thermosetting resins such as epoxy resins and maleimide resins; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The curing agent is used for deep-part curing and for improving mechanical strength, and specific examples thereof include polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, and the like.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, and the like.

The above curing agent may be used in combination with a co-curing compound capable of ring-opening polymerizing the oxetane skeleton of the oxetane compound together with the curing agent. Examples of the curing assistant compound include polycarboxylic acids, polycarboxylic acid anhydrides, and acid generators. The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used for further improving the film formability of the photosensitive resin composition, and a silicone surfactant, a fluorine surfactant, or the like is preferably used.

Examples of the silicone-based surfactant include commercially available silicone surfactants such as DC3PA, DC7PA, SH11PA, SH21PA and SH8400 available from dow corning dongli silicone corporation; TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 of GE Toshiba Silicone company, and the like. Examples of the fluorine-based surfactant include commercially available MEGAFAC F-470, F-471, F-475, F-482, F-489 and F-554 (Dainippon ink chemical industries, Ltd.); BM-1000, BM-1100(BM Chemie Co.); FLUORAD FC-135/FC-170C/FC-430 (Sumitomo 3M strain), and the like. The above-exemplified surfactants may be used each alone or in combination of two or more.

The adhesion promoter is an additive used for improving coatability and adhesion to a substrate, and may include a silane coupling agent containing a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof.

Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid, gamma-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

Specific examples of the antioxidant include 2,2' -thiobis (4-methyl-6-tert-butylphenol) and 2, 6-di-tert-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

Specific examples of the anti-gelling agent include sodium polyacrylate and the like.

The additives not contained in the above-mentioned additives may be appropriately added to the composition by those skilled in the art within a range not impairing the effects of the present invention. For example, the additive may be used in an amount of 0.05 to 10 wt%, preferably 0.1 to 10 wt%, more preferably 0.1 to 5 wt% based on 100 wt% of the entire black photosensitive resin composition, but is not limited thereto.

The black photosensitive resin composition according to one embodiment of the present invention has an advantage that it can be cured at a low temperature and is advantageous when applied to a flexible substrate.

Specifically, the black photosensitive resin composition can be cured at 100 ℃ or lower, for example, 80 to 100 ℃. The cured film obtained by curing the black photosensitive resin composition at 80 to 100 ℃ may be immersed in Propylene Glycol Monomethyl Ether Acetate (PGMEA) at 90 ℃ for 10 minutes, and the film retention may be 80% or more.

The method for producing the black photosensitive resin composition of the present invention is not particularly limited, and the method for producing the black photosensitive resin composition known in the art is used.

For example, it can be obtained by adding a colorant to a solvent, adding the remaining components and other additives, and stirring. In this case, the colorant may be added in the form of a paste prepared by dissolving or dispersing a pigment or the like in a solvent or an alkali-soluble resin in advance. When the additive is in the form of a solution, it may be previously added to the solvent together with the colorant.

The black photosensitive resin composition thus produced can be preferably used for producing a black matrix of an image display device. The black matrix is a concept including a spacer for maintaining a cell gap (cell gap), a black column spacer (black matrix integrated spacer), and the like.

Accordingly, one embodiment of the present invention relates to a black matrix formed using the black photosensitive resin composition.

A typical patterning process for forming a black matrix according to a photolithography method includes:

a) a step of coating a substrate with a black photosensitive resin composition;

b) a pre-baking step of drying the solvent;

c) irradiating the obtained coating film with active light through a photomask to cure the exposed portion;

d) a step of performing a developing step of dissolving the unexposed portion with an alkali aqueous solution; and

e) the steps of drying and postbaking are carried out.

The substrate is a glass substrate or a polymer plate. As the glass substrate, soda lime glass, barium-or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, or the like can be used particularly preferably. Examples of the polymer sheet include polycarbonate, acryl, polyethylene terephthalate, polyether sulfide, polysulfone, and the like.

In this case, coating can be performed by a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit coater (also referred to as a die coater), or a spray printer in order to obtain a desired thickness.

In the prebaking, heating is performed by an oven, a hot plate, or the like. In this case, the heating temperature and the heating time in the prebaking are appropriately selected depending on the solvent used, and are carried out, for example, at 80 to 150 ℃ and preferably at 80 to 100 ℃ for 1 to 30 minutes.

The exposure after the prebaking is performed by an exposure machine, and exposure is performed through a photomask, so that only a portion corresponding to the pattern is exposed to light. In this case, for example, visible light, ultraviolet light, X-rays, electron beams, and the like can be used as the light to be irradiated.

The alkali development after the exposure is performed for the purpose of removing the colored photosensitive resin composition in the non-exposed portion, and a desired pattern is formed by the development. As a developer suitable for the alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal can be used. In particular, the treatment is carried out by using an aqueous alkaline solution containing 1 to 3 wt% of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate at a temperature of 10 to 50 ℃, preferably 20 to 40 ℃ by using a developing machine, an ultrasonic cleaning machine or the like.

The post-baking is performed to improve the degree of curing of the patterned film and to improve the reflow of the taper angle of the pattern, and is performed by heat treatment at 80 to 100 ℃ for 10 to 120 minutes. The post-baking is performed by an oven, a hot plate, or the like as in the pre-baking.

One embodiment of the present invention relates to an image display device including the black matrix.

The image display device of the present invention includes a configuration known in the art, in addition to the black matrix described above. That is, the image display device to which the black matrix of the present invention is applicable is included in the present invention. For example, a transmissive liquid crystal display device is known in which a liquid crystal layer is formed by opposing counter electrode substrates each including a thin film diode (TFT element), a pixel electrode, and an alignment layer at a predetermined interval and injecting a liquid crystal material into the gap. In addition, there is also a reflective liquid crystal display device in which a reflective layer is provided between a substrate of a color filter and a colored layer. As another example, there is a liquid crystal display device including a Thin Film Transistor (TFT) substrate mounted on a transparent electrode of a color filter, and a backlight fixed at a position where the TFT substrate overlaps the color filter.

The present invention will be described in more detail below with reference to examples, comparative examples, and experimental examples. It is apparent to those skilled in the art that these examples, comparative examples, and experimental examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Synthesis example 1: production of alkali-soluble resin (B-1)

In a 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was made to flow at 0.02L/min to prepare a nitrogen atmosphere, and then 150g of diethylene glycol methyl ethyl ether was added and heated to 70 ℃ with stirring. Then, 3, 4-epoxy tricyclo [5.2.1.0 ]^2,6]Decane-9-yl acrylate with 3, 4-epoxytricyclo [5.2.1.0^2,6]Mixture of decane-8-yl acrylate [50:50 (molar ratio)]And 0.30mol, 0.50mol, and 0.20mol were dissolved in 150g of diethylene glycol methyl ethyl ether so that the total amount of glycidyl methacrylate and acetic acid became 1mol, respectively, to prepare solutions. The prepared solution was dropped into a flask using a dropping funnel, and then a solution in which 27.9g (0.11mol) of 2,2' -azobis (2, 4-dimethylvaleronitrile), which is a polymerization initiator, was dissolved in 200g of diethylene glycol methyl ethyl ether was dropped into the flask using another dropping funnel over 4 hours. After the completion of the dropwise addition of the polymerization initiator solution, the solution was maintained at 70 ℃ for 4 hours, and then cooled to room temperature, thereby producing an alkali-soluble resin (B-1).

Production example 1: production of colorant Dispersion liquid (A-1)

A colorant dispersion (A-1) was produced by mixing and charging a composition comprising the following components in a weight ratio of 50:50 with a rigid grinding medium (zirconia beads) having an average particle size of 0.1mm, and then dispersing a pigment for 4 to 6 hours by a bead mill: 15.0% by weight of an organic black pigment (IrgaphorS 100CF, Basff Corp.), 3% by weight of the alkali-soluble resin synthesized in Synthesis example 1 above as a dispersion resin, 2.5% by weight of an acrylic polymer dispersant (DISPERBYK-2000, NV. about.40.0%) as a dispersant, and 79.5% by weight of propylene glycol monomethyl ether acetate as a solvent.

Examples and comparative examples: production of Black photosensitive resin composition

The respective components were mixed according to the composition of table 1 below to produce a black photosensitive resin composition (wt%).

[ Table 1]

A-1: preparation example 1 colorant Dispersion

B-1: synthesis of alkali-soluble resin of example 1

C-1: ethoxylated pentaerythritol tetraacrylate (ATM-4E, Xinzhongcun)

C-2: mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (A-TMM-3LMN, Xinzhongcun)

C-3: trimethylolpropane trimethacrylate

C-4: ethoxylated dipentaerythritol hexaacrylate (A-DPH-12E, New Zhongcun chemical)

C-5: dipentaerythritol hexaacrylate (DPHA, Japan chemical)

C-6: poly pentaerythritol polyacrylate (A-TPE-30-NS, Xinzhongcun)

D-1: PBG-327(Tronly corporation)

E-1: celloxide2021P (Dailuo Co., Ltd.)

F-1: pentaerythritol tetrakis (3-mercaptopropionate)

H-1: f554(DIC Co., Ltd.)

G-1: propylene Glycol Monomethyl Ether Acetate (PGMEA)

Experimental example 1: evaluation of physical Properties of colored substrate

A5 cm by 5cm glass substrate (Corning Corp.) was washed with a neutral detergent and water and dried. The black photosensitive resin compositions produced in the comparative examples and examples were each spin-coated on the glass substrate so that the final film thickness became 2.0 μm, and the solvent was removed by pre-baking at 80 ℃, i.e., drying for 2 minutes. Then, a mask containing a line pattern was used to expose 100mJ/cm²The resultant was exposed to light, developed, and then fired at 100 ℃ for 1 hour to form a line pattern.

(1) Taper angle

A cross section of a 20 μm pattern was cut out of the line pattern of the substrate fabricated by the above method, and the taper angle was observed by SEM (HITACHI) corporation, SU-8100). The results are shown in table 2 below.

(2) Solvent resistance

The substrate prepared by the above method was immersed in PGMEA at 90 ℃ for 10 minutes, and then the height difference (Δ) of the 100 μm pattern before and after the immersion was measured. The results of solvent resistance evaluation according to the following evaluation criteria are shown in table 2 below.

< evaluation criteria >

Very good: the height difference before and after impregnation is less than 0.2 μm

O: the height difference before and after impregnation is more than 0.2 μm and less than 0.4 μm

X: the height difference before and after impregnation is more than 0.4 μm

(3) Adhesion Property

For the substrate fabricated by the above method, the pattern of the minimum size left on the substrate was confirmed using an optical microscope. The adhesion evaluation results according to the following evaluation criteria are shown in table 2 below.

< evaluation criteria >

O: maintaining a pattern of less than 5 μm

And (delta): maintaining a pattern of 5 μm or more and less than 9 μm

X: disappearance of pattern of 9 μm or more

[ Table 2]

From table 2 above, it was confirmed that the black photosensitive resin compositions of examples 1 to 3, which comprise an epoxy compound and a compound having a thiol group and which comprise a photopolymerizable compound having 4 or less functional groups as the photopolymerizable compound, exhibited positive taper angles even when fired at a low temperature of 100 ℃.

On the other hand, the black photosensitive resin compositions of comparative examples 1 to 5, which contained only a photopolymerizable compound having a functionality of more than 4 as a photopolymerizable compound or did not contain any of an epoxy compound and a compound having a thiol group, exhibited reverse taper angles or exhibited defects in one or more of solvent resistance and adhesion at the time of low-temperature firing.

While certain features of the invention have been described in detail above, it will be apparent to those skilled in the art that this detailed description is merely a preferred embodiment, and that the scope of the invention is not limited thereto. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above-described contents.

It is therefore intended that the actual scope of the invention be defined by the scope of the appended claims and their equivalents.