TWI654487B - Black photosensitive resin composition, black matrix using same, and image display device comprising the black matrix - Google Patents

Abstract

Disclosed is a black photosensitive resin composition, a black matrix prepared from the black photosensitive resin composition, and an image display device in which the matrix is mounted. The black photosensitive resin composition has excellent adhesion to a substrate, and can form a micro pattern suitable for realizing high-resolution display.

Description

Black photosensitive resin composition, black matrix and image display device Technical field

The present invention relates to a black photosensitive resin composition which has excellent adhesion to a substrate and which can form a micro-pattern suitable for realizing high-resolution display; A black matrix prepared from a photosensitive resin composition; and an image display device including the black matrix.

Background technique

The image quality of the display depends on the color filter. A black dot pattern (referred to as a black matrix) is placed between the color pixels of the color filter. In order to achieve a large screen area and high contrast, the black matrix of the color filter needs to be patterned with high resolution with sufficient light shielding.

Conventional black matrices use chromium. To this end, chromium is deposited on the entire surface of the glass substrate and patterned by etching. However, this process has the disadvantage of high cost and high reflectivity inherent to chromium. In addition, such a method causes environmental pollution due to chromium waste liquid. Therefore, active research is being conducted on a resin black matrix using a pigment dispersion method in which the pigment dispersion method can be microscopically Min processing.

In addition, research has progressed toward the preparation of black compositions from other colored pigments other than carbon black. Due to its poor light-shielding properties, other coloring pigments other than carbon black should be used in an extremely high ratio to obtain a black composition. However, such black compositions tend to have increased viscosity and are difficult to handle. Further, the film formed of the black composition has low strength or poor adhesion to the substrate. Therefore, various studies are being conducted in order to meet the demand for performance improvement in the art.

As the display becomes lighter and thicker and the need for large areas increases, the technique of minimizing the coalescing components between the upper and lower plates in the display module is applied, thereby widening the screen by even 1 inch. In particular, as the mobile market has gradually increased, in order to maximize mobility characteristics, strategies for miniaturizing mobile devices and maximizing displays while making the modules themselves thin and light are being considered.

One such strategy is to coalesce in new ways rather than agglomerate in the usual way. In the conventional method, the edge of the glass plate and the edge of the black matrix are coalesced at the same time, but the display efficiency in the panel is deteriorated because a glass plate larger than the actual one is used. As an alternative to improving display efficiency, coalescence is performed only in the black matrix portion without using glass. In this regard, a card-type adhesive is used to ensure process characteristics.

However, the conventional method has no significant problem for the pressure of coalescence during the reliable process and the adhesiveness of the sealant because both the glass and the black matrix are used. In contrast, when coalescing with a card-type binder is used only in the black matrix portion, the pressure applied during coalescence and the adhesion of the black matrix to the substrate may be problematic during a reliable process, and cause sealing. Piece and conductive film damage. In addition, the method of using a card-type adhesive has the disadvantage of not meeting the requirements of high optical density (OD) and substrate adhesion.

Korean Patent No. 10-1068622 discloses a black matrix photosensitive resin composition having high light-shielding properties and improved adhesive properties, but the composition has a problem that high resolution cannot be achieved.

Korean Patent No. 10-0671106 discloses a black matrix composition having improved durability and photosensitivity, the black matrix composition comprising a card-type binder and a specific initiator. The specific initiator includes an acetophenone initiator and a benzophenone initiator, but does not guarantee a sufficient effect of improving sensitivity.

[Related field documents] [Patent Document]

(Patent Document 1) Korean Patent No. 10-1068622

(Patent Document 2) Korean Patent No. 10-0671106

Summary of invention

Through extensive and in-depth research on the black matrix, it has been found that the use of a cardo-based resin together with a quinone-based initiator ensures excellent durability and high resolution of the black matrix, thereby producing the present invention.

Accordingly, it is an object of the present invention to provide a black photosensitive resin composition which can ensure excellent adhesion and high resolution.

Another object of the present invention is to provide a black matrix prepared from the above black photosensitive resin composition.

It is still another object of the present invention to provide an image display apparatus including the above black matrix.

In order to achieve the above object, the present invention provides a black photosensitive resin composition comprising: an alkali-soluble binder resin, a photopolymerizable compound, a photopolymerization initiator, a black pigment, and a solvent, wherein The alkali-soluble binder resin includes a card-type binder resin, and the photopolymerization initiator includes at least one compound represented by the following Chemical Formula 1:

Wherein R ₁ to R ₁₀ and p are as described in the specification.

In one embodiment, the card multi-type binder resin has at least one repeating unit of the following Chemical Formula 2 and Chemical Formula 3:

Wherein R ₂₄ to R ₂₆ are as defined in the specification.

Further, the present invention provides a black photosensitive resin composition A black matrix prepared, and an image display device including the above black matrix.

The black photosensitive resin composition according to the present invention overcomes the problems associated with the adhesion and resolution of the conventional composition.

The black matrix prepared from the above black photosensitive resin composition exhibits excellent adhesion to a substrate, and can accurately form a micro pattern, thereby ensuring high resolution of a vivid image.

Figure 1 shows the results of the adhesion test shown by the peeling of the left side panel and the peeling of the right side panel.

Figure 2 shows the minimum pattern obtained in the adhesion test at the time of development.

detailed description

According to an aspect of the invention, the present invention provides a black photosensitive resin composition which is applicable to a black matrix of an image display device.

Specifically, the black photosensitive resin composition of the present invention may mainly include a card-type binder resin as an alkali-soluble resin, and an oxime ester compound as a photopolymerization initiator. The card-type binder resin is excellent in adhesion to the substrate, durability, and heat resistance, and the oxime ester-based initiator has excellent photosensitivity, so that the black matrix can enhance adhesion during development of the micro-pattern. Further, the black matrix prepared from the above black photosensitive resin composition can advantageously and easily form a micro pattern.

The black photosensitive resin composition according to the present invention may further comprise a photopolymerizable compound, black, in addition to the card-type binder and the oxime-based initiator. Pigments and solvents.

Hereinafter, each component of the black photosensitive resin composition will be described.

The alkali-soluble binder resin reacts with light or heat and functions as a dispersion medium of a black pigment. Further, as the name implies, the alkali-soluble binder resin should be dissolved in an alkaline developer which is used in the development stage during the manufacture of the black matrix.

In one embodiment of the present invention, the alkali-soluble binder resin may be a card-type binder having at least one repeating unit of the following Chemical Formula 2 and Chemical Formula 3. Since the adhesion to the substrate is improved, the alkali-soluble binder resin contributes to the adhesiveness required for development, so that a high-resolution micropattern can be obtained.

Wherein R ₂₄ and R ₂₅ each independently represent a hydrogen atom, a halogen or an alkyl group of 1 to 5 carbon atoms; R ₂₆ represents a hydrogen atom or a methyl group; and X represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-fluorenyl or a single bond; Y represents an acid anhydride residue; Z represents The acid dianhydride residue; and the molar ratio (m/n) between the various structural units is from 0/100 to 100/0.

In Chemical Formula 2 and Chemical Formula 3, R ₂₄ and R ₂₅ are each independently a hydrogen atom, a halogen atom or an alkyl group of 1 to 5 carbon atoms; and R ₂₆ is a hydrogen atom or a methyl group. Preferably, R ₂₄ to R ₂₆ are each a hydrogen atom.

For the card multi-type binder of the present invention, the repeating unit represented by Chemical Formula 2 or Chemical Formula 3 may include: when X is -CO-, bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5) -Dimethylphenyl)one or bis(4-hydroxy-3,5-dichlorophenyl)one; when X is -SO ₂ -, bis(4-hydroxyphenyl)anthracene, bis(4-hydroxyl) -3,5-dimethylphenyl)anthracene or bis(4-hydroxy-3,5-dichlorophenyl); when X is -C(CF ₃ ) ₂ -, bis(4-hydroxyphenyl) Hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane or bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane; when X is -Si(CH) ₃ ) _2- , bis(4-hydroxyphenyl)dimethyl decane, bis(4-hydroxy-3,5-dimethylphenyl)dimethyl decane or bis(4-hydroxy-3,5- Dichlorophenyl)dimethyloxane; when X is -CH ₂ -, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane or bis(4- Hydroxy-3,5-dibromophenyl)methane; when X is -C(CH ₃ ) ₂ -, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy- 3,5-Dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl) Propane or 2,2-bis(4-hydroxy-3-chlorophenyl)propane; When X is -O-, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether or bis(4-hydroxy-3,5-dichlorophenyl) Ether; when 9 is 9,9-fluorenyl, 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9 - bis(4-hydroxy-3-chlorophenyl)anthracene, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorophenyl)anthracene 9,9-bis(4-hydroxy-3-methoxyphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis (4 -hydroxy-3,5-dichlorophenyl)anthracene or 9,9-bis(4-hydroxy-3,5-dibromophenyl)anthracene; and when X is a single bond, 4,4'-bisphenol Or 3,3'-bisphenol.

In Chemical Formula 2, Y and Z are an acid anhydride residue and an acid dianhydride residue, respectively, and can be introduced by reacting a synthesis intermediate of the card-type binder resin of the present invention with an acid anhydride and an acid dianhydride, respectively. Examples of the acid anhydride for introducing the Y residue include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endoscope Tetrahydrophthalic anhydride, chloric anhydride and methyltetrahydrophthalic anhydride. The acid dianhydride used to introduce the Z residue may be an aromatic dicarboxylic anhydride such as pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and diphenyl ether tetracarboxylic acid. Diacid anhydride.

The card multi-type binder resin of the present invention can be prepared by the following process: First, a bisphenol oxime type epoxy compound (which can be synthesized from bisphenol oxime) is reacted with a (meth) acrylate to produce a bisphenol oxime type epoxy acrylate compound. Subsequently, it is reacted with an acid anhydride, an acid dianhydride or a mixture thereof in a cellosolve such as ethyl cellosolve acetate or butyl cellosolve acetate under heating. In this reaction, an acid anhydride, an acid dianhydride or a mixture thereof is used to introduce Y and Z. In practice, the mixture of anhydride and acid dianhydride is preferably reacted with a bisphenolphthalein type epoxy acrylate. Further, the kind of the (meth) acrylate is not particularly limited. Any (meth) acrylate known in the art can be used in the present invention. Preferred Yes, the reaction stoichiometry was set to 0.5 mol of an acid anhydride per 1 mol of the epoxy acrylate resin. Further, the reaction temperature is preferably from 100 to 130 ° C, and preferably from 115 to 125 ° C.

When the card-type binder resin of the present invention has both of the repeating units of Chemical Formula 2 and Chemical Formula 3, the molar ratio (m/n) between the two repeating units of Chemical Formula 2 and Chemical Formula 3 is not particularly limited, but It is preferably from 1/99 to 90/10, and more preferably from 5/95 to 80/20. If the molar ratio m/n is within this range, the binder resin maintains an appropriate carboxylic acid content therein, thereby maintaining excellent alkali resistance. Therefore, the binder resin prevents the developer from eluting into the exposed region, and exhibits an excellent alkali developing ability, so that a micro pattern can be formed. Further, the card-type binder resin having the above molar ratio has no viscosity problem after initial curing, and contact exposure can be applied. In addition, the film obtained after the post-curing is excellent in heat resistance, so that it can be used for ITO sputtering even at temperatures as high as 250 °C.

The molecular weight of the card-type binder resin according to the present invention is expressed as an intrinsic viscosity (ηnh), wherein the intrinsic viscosity (ηnh) is 0.5 g of a card-type binder measured in 100 ml of N-methylpyrrolidone at 30 ° C. The intrinsic viscosity of the solution. Its intrinsic viscosity is 0.1 dl/g or more, and preferably 0.15 dl/g or more. When the intrinsic viscosity is less than 0.1 dl/g, the molecular weight of the card-type binder resin is too small, and the viscosity problem after the initial curing cannot be avoided. Because of this, the card-type adhesive resin cannot be used for contact exposure and may be a cause of mask contamination.

The cardo type binder resin may be used in an amount of 1 to 40% by weight, and preferably 5 to 20% by weight, based on 100% by weight of the total composition. Within this range, The card-type binder resin is sufficiently dissolved in the developer to promote the formation of a pattern and prevent the film from being thinned at the pixels of the exposed region, thereby improving the defect at the non-pixel portion.

An oxime ester initiator (which is a feature of the present invention) is used together with a card-type binder to enhance the sensitivity of the black photosensitive resin composition. The photopolymerization initiator is a compound for triggering a reaction of a photopolymerizable compound. In the present invention, in order to improve the pattern and high resolution, an oxime ester-based initiator represented by the following Chemical Formula 1 is used as a photopolymerization initiator to make the black photosensitive resin composition highly sensitive to light.

Wherein R ₁ to R ₃ are each independently hydrogen, halogen, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, and 7 to 40 An arylalkyl group of a carbon atom, a hydroxyalkyl group of 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group of 2 to 40 carbon atoms or a cycloalkyl group of 3 to 20 carbon atoms; each of R ₄ to R ₁₀ Independently hydrogen, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, 1~ a hydroxyalkyl group of 20 carbon atoms, a hydroxyalkoxyalkyl group of 2 to 40 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an amine group, a nitro group, a cyano group or a hydroxyl group; and p is 0 or 1.

As used herein, the term "halogen" is used to encompass fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

As used herein, the term "alkyl" refers to a straight or branched hydrocarbon group consisting solely of a hydrogen atom and a carbon atom, the linear or branched hydrocarbon group having no unsaturation and being attached to the remainder of the molecule via a single bond. . The alkyl group is preferably a linear or branched alkyl group of 1 to 20 carbon atoms, more preferably a linear or branched alkyl group of 1 to 10 carbon atoms, and most preferably 1 to 6 carbon atoms. A linear or branched alkyl group. Examples of such unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl groups. At least one hydrogen atom of the alkyl group may be substituted with a halogen atom, a hydroxyl group, a fluorenyl group (-SH), a nitro group, a cyano group, a substituted or unsubstituted amino group, a fluorenyl group, a hydrazine or a hydrazine, a carboxyl group, a sulfonate. Acid, phosphoric acid, alkyl group of 1 to 20 carbon atoms, haloalkyl group of 1 to 20 carbon atoms, alkenyl group of 1 to 20 carbon atoms, alkynyl group of 1 to 20 carbon atoms, 1 to 20 carbon atoms a heteroalkyl group, an aryl group of 6 to 20 carbon atoms, an arylalkyl group of 6 to 20 carbon atoms, a heteroaryl group of 6 to 20 carbon atoms or a heteroarylalkyl group of 6 to 20 carbon atoms.

Preferably, the alkoxy group referred to herein is a linear or branched alkyl group bonded to an oxygen single bond of 1 to 20 carbon atoms. The alkoxy group is more preferably an alkoxy group of 1 to 10 carbon atoms, and most preferably an alkoxy group of 1 to 4 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a t-butoxy group. The alkoxy group may be substituted by one or more halogen atoms to give a haloalkoxy group such as a fluoroalkoxy group, a chloroalkoxy group or a bromoalkoxy group. Haloalkoxy includes: fluoromethoxy, chloromethoxy, trifluoromethoxy, triple Fluoroethoxy, fluoroethoxy and fluoropropoxy. One or more hydrogen atoms of the alkoxy group may be substituted with the substituents mentioned in the alkyl group.

As used herein, the term "cycloalkyl" is used to encompass both polycyclic hydrocarbons and monocyclic hydrocarbons. At least one hydrogen atom of the cycloalkyl group may be substituted with a substituent mentioned in the alkyl group. The cycloalkyl group may preferably have 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and most preferably 3 to 8 carbon atoms.

As used herein, the term "aryl" is used to include an aromatic monocyclic system or an aromatic polycyclic ring system consisting solely of hydrogen atoms and carbon atoms. At least one hydrogen atom of the aryl group may be substituted with a substituent mentioned in the alkyl group. In the context of an organic molecule, an aryl group refers to any functional group derived from an aromatic hydrocarbon by eliminating one hydrogen atom therefrom. As described above, the aryl group of the present invention may be monocyclic or polycyclic, fused or separated, and each ring is a 4 to 7 membered ring, preferably a 5-membered ring or a 6-membered ring. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 18 carbon atoms.

As used herein, the term "hydroxyalkyl" refers to an alkyl group bonded to a hydroxy group, ie, OH-alkyl; and the term "hydroxyalkoxyalkyl" refers to a hydroxyalkane bonded to an alkyl group via an oxygen atom. Base, ie, hydroxy-O-alkyl. The hydroxyalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and most preferably 1 to 6 carbon atoms. The hydroxyalkoxyalkyl group preferably has 2 to 40 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 2 to 9 carbon atoms.

As used herein, the term "arylalkyl" refers to an alkyl group wherein at least one of the hydrogen atoms is replaced by an aryl group. The arylalkyl group preferably has 7 to 40 carbon atoms, more preferably 7 to 28 carbon atoms, and most preferably 7 to 24 carbon atoms.

For the application of the present invention, an oxime ester initiator is represented as chemistry Formula 1, wherein p is 0 or 1. When p is 0 or 1, the oxime ester-based initiator may be represented by the following Chemical Formula 4 or Chemical Formula 5, respectively.

Wherein R ₁₁ to R ₁₃ are each independently a hydrogen atom, a halogen atom, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, 7~ An arylalkyl group of 40 carbon atoms, a hydroxyalkyl group of 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group of 2 to 40 carbon atoms or a cycloalkyl group of 3 to 20 carbon atoms; and A is hydrogen An alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, and 1 to 20 carbon atoms A hydroxyalkyl group, a hydroxyalkoxyalkyl group of 2 to 40 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an amine group, a nitro group, a cyano group or a hydroxyl group.

Specific examples of the groups R ₁₁ to R ₁₃ include, but are not limited to, hydrogen, bromine, chlorine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, N-pentyl, isopentyl, n-hexyl, isohexyl, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, fluorenyl, penanthryl, methoxy, ethoxy, n-propyl Oxygen, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxy-n-pentyl , hydroxyisopentyl, hydroxy-n-hexyl, hydroxyisohexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxy Ethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl and hydroxyethoxyhexyl.

Specific examples of the group A include, but are not limited to, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, naphthyl, biphenyl, Terphenyl, decyl, decyl, phenanthryl, methoxy, ethoxy, propoxy, butoxy, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxymethoxy Base, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl , amine, nitro, cyano and hydroxyl.

Preferably, R ₁₁ is hydrogen or n-butyl; R ₁₂ is methyl; R ₁₃ is methyl, n-butyl or phenyl; A is hydrogen or nitro.

Representative oxime ester initiators useful in the present invention are the following compounds, but are not limited thereto. Any compound known in the art can be used as long as the conditions defined above are met.

[Chemical Formula 5] Wherein R ₁₄ to R ₂₃ are each independently a hydrogen atom, a halogen atom, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, 7~ An arylalkyl group of 40 carbon atoms, a hydroxyalkyl group of 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group of 2 to 40 carbon atoms or a cycloalkyl group of 3 to 20 carbon atoms.

Specific examples which may be used for R ₁₄ to R ₂₃ include: hydrogen, bromine, chlorine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, Isoamyl, n-hexyl, isohexyl, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, fluorenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy , n-butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxy-n-pentyl, hydroxyisopentyl, hydroxy n-Hexyl, hydroxyisohexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxy Ethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl and hydroxyethoxyhexyl.

Preferably, R ₁₄ may be hydrogen, methyl, ethyl, propyl or butyl; R ₁₅ may be methyl, ethyl or propyl; R ₁₆ may be methyl, ethyl, propyl or butyl; R ₁₇ to R ₂₃ may be hydrogen.

Representative oxime ester initiators useful in the present invention are the following compounds, but are not limited thereto. As long as the conditions defined above are met, known in the art Any compound can be used.

The photopolymerization initiator may be used in an amount of 0.1 to 12% by weight, and preferably 0.5 to 5% by weight, based on 100% by weight of the black photosensitive resin composition. When the amount of the photopolymerization initiator used is less than the lower limit, the composition has a poor sensitivity so that the pattern may be delaminated during development. On the other hand, when the amount used is larger than the upper limit, the photopolymerization initiator causes an excessive crosslinking reaction, resulting in deterioration of film properties such as wrinkling.

In the case where there is no adverse effect on the effects of the present invention, an additional photopolymerization initiator can be used. The additional photopolymerization initiator which can be used in the present invention may preferably be at least one selected from the group consisting of an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, and a thioxanthone compound.

Examples of the acetophenone compound include: diethoxyacetophenone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1- Ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamine 1-(4-morpholinylphenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one And 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butan-1-one.

Examples of the benzophenone compound include: benzophenone, methyl o-benzolobenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide , 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone.

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-piperidin-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3 , 5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine.

Examples of the biimidazole compound include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxybenzene) Bi)imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, 2,2-bis (2,6 -dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and at 4, 4' An imidazole compound having a phenyl group substituted with a carboalkoxy group at the 5-, and 5-positions. Preferred is 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2' -biimidazole.

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

The photopolymerization initiator may further include an auxiliary agent for increasing the sensitivity of the black photosensitive resin composition according to the present invention. The auxiliary agent can improve productivity by further increasing the sensitivity of the black photosensitive resin composition.

As the auxiliary agent, at least one selected from the group consisting of an amine compound, a carboxylic acid compound, and a mercapto group-containing organic sulfur compound can be preferably used.

Examples of the amine compound include: aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; and aromatic amine compounds such as methyl 4-dimethylaminobenzoate, 4-dimethyl Ethyl benzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-di Methyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as "milaconone") and 4,4'-bis(diethylamino)benzol A ketone, of which an aromatic amine compound is preferred.

The carboxylic acid compound may be an aromatic heteroacetic acid, and examples thereof include: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylbenzene Thioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylacetic acid, phenoxyacetic acid, Naphthylthioacetic acid, N-naphthylglycine, and naphthyloxyacetic acid.

Examples of the mercapto group-containing organic sulfur compound include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutylphosphonium) -1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate) ), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).

The amount of the auxiliary agent used per 1 mole of the photopolymerization initiator is usually 10 moles or less, and preferably 0.01 to 5 moles. If it is within this range, the above-mentioned auxiliary agent is expected to promote polymerization efficiency and increase productivity.

The black photosensitive resin composition according to the present invention may further include a photopolymerizable compound in addition to the card-type binder resin and the oxime ester-based initiator.

For use in strengthening the pattern strength, the photopolymerizable compound useful in the present invention may be a monofunctional monomer, a difunctional monomer or a polyfunctional monomer, of which a difunctional monomer is preferred.

There is no particular limitation on the kind of the monofunctional monomer. The monofunctional monomer may include: mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.

There is no particular limitation on the kind of the bifunctional monomer. For example, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(methyl) can be used. ) acrylate, bis(acryloxyethyl)ether of bisphenol A or 3-methylpentanediol di(meth)acrylate.

Useful in the present invention without particular limitation on the kind thereof Examples of the polyfunctional monomer may be: trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane III ( Methyl) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol tri(meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol Hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

The photopolymerizable compound can be used in an amount of 1 to 20% by weight, and preferably 1 to 10% by weight, based on 100% by weight of the black photosensitive resin composition. For example, if the content of the photopolymerizable compound is less than the lower limit, the black photosensitive resin composition is inferior in sensitivity to light. On the other hand, the content higher than the upper limit of the photopolymerizable compound provides excessive adhesion to the photosensitive resin layer, so that the strength of the film is insufficient, and the pattern may be lost during development.

The black pigment usable in the present invention may be carbon black, an organic black pigment, a titanium block, or may be a mixture of a red pigment, a green pigment, and a blue pigment.

In detail, a black pigment can be used as a coloring dispersant obtained by mixing and grinding carbon black and two or more coloring pigments. Examples of usable carbon black include: CHBK-17 from Mikuni Color Ltd.; SEAST 5HIISAF-HS, SEAST KH, SEAST 3HHAF manufactured by Tokai Carbon Ltd. HS, SEAST NH, SEAST 3M, SEAST 300HAF-LS, SEAST 116HMMAF-HS, SEAST 116MAF, SEAST FMFEF-HS, SEAST SOFEF, SEAST VGPF, SEAST SVHSRF-HS and SEAST SSRF; DIAGRAM BLACK II, DIAGRAM BLACK N339, DIAGRAM BLACK SH, DIAGRAM BLACK H, DIAGRAM LH, DIAGRAM HA, DIAGRAM SF, DIAGRAM N550M, DIAGRAM M, manufactured by Mitsubishi Chemical Corporation DIAGRAM E, DIAGRAM G, DIAGRAM R, DIAGRAM N760M, DIAGRAM LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47,#45,#45L,#25,#CF9,#95,#3030,#3050,MA7,MA77,MA8,MA11,OIL7B,OIL9B,OIL11B,OIL30B and OIL31B; by Degussa Japan Ltd. ( PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX manufactured by Degussa Japan Co., Ltd. -35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100 and LAMP BLACK- 101; and RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RA manufactured by Columbia Carbon VEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN- 520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN- 1190ULTRA and RAVEN-1170.

Useful pigments in the form of a mixture with carbon black include: Carmine 6B (CI12490), Phthalocyanine Green (CI74260), Phthalocyanine Blue (CI74160), MITSUBISHI Carbon Black MA100, Perylene Black (BASF) K0084.K0086), Cyanine Black, Linolyellow (CI21090), Linolyellow GRO (CI21090), Benzidine Yellow 4T-564D, MITSUBISHI Carbon Black MA-40, Victoria Pure Blue (CI42595), CI Pigment Red 97, 122, 149, 168, 177, 180, 192, 215, CI Pigment Green 7, 36, CI Pigment 15: 1, 15: 4, 15: 6, 22, 60, 64, CI Pigment 83, 139 , and CI Pigment Violet 23. In addition, white pigments and fluorescent pigments can be used.

Any carbon black known in the art can be used as long as it can shield the light. Representative carbon blacks are channel black, furnace black, thermal black and lamp black.

In addition, resin-coated carbon black can be used as the black pigment. The resin-coated carbon black has a lower electrical conductivity than the bare carbon black, and thus provides better electrical insulation when forming a black matrix or a black column spacer.

A black pigment is used in the form of a pigment dispersant in which a black pigment of the same diameter is uniformly dispersed. For example, a pigment dispersant is used to uniformly disperse the same pigment. Therefore, a pigment in which the pigment is uniformly dispersed can be obtained Dispersant.

For use in the present invention, the pigment dispersant may be a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a polyester surfactant or a polyamine surfactant. These surfactants may be used singly or in combination.

Further, an acrylate type dispersant may be preferably used, including: butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). Acrylate dispersants are commercially available, for example, under the trade names DISPER BYK-2000, DISPER BYK-2001, BYK DISPER-2070 or DISPER BYK-2150. These acrylate-based dispersants may be used singly or in combination.

A pigment dispersant different from the type of the resin of the acrylate type dispersant can be used. Other resin type pigment dispersants useful in the present invention are known in the art, and may be, for example, oily dispersants such as polyurethanes, polycarboxylates represented by polyacrylates, and unsaturated polycondensates. Indoleamine, polycarboxylic acid, (partial) amine salt of polycarboxylic acid, ammonium salt of polycarboxylic acid, alkylamine salt of polycarboxylic acid, polyoxyalkylene oxide, long chain polyamine guanamine phosphate, hydroxyl group Polycarboxylate and modified product thereof, or decylamine formed by reacting a polyester having a free carboxyl group with poly(lower alkyleneimine) or a salt thereof; a water-soluble resin or a water-soluble polymer compound, such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; polyester; modified poly Acrylate; an adduct of ethylene oxide/propylene oxide; and a phosphate ester. For cationic forms, resin type pigment dispersants are commercially available, for example, from BYK Chemie. Product name DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; purchased from BASF Trade names EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330 EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; trade names SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; HINOACT T-6000 from Kawaken Fine Chemicals, HINOACT T-7000, HINOACT T-8000; trade names AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823 from Ajinomoto; FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA from Kyoeisha Chemical -33, FLORENE DOPA-44. Other types of pigment dispersants may be used singly or in combination or in the form of a mixture with an acrylate dispersant.

The black pigment may be used in an amount of 5 to 20% by weight, and preferably 5 to 10% by weight, based on 100% by weight of the black photosensitive resin composition. If the black pigment is present at a level below the lower limit, the above composition cannot be used for the black matrix. On the other hand, as with the content reduction of other components, the content of the black pigment exceeding the upper limit deteriorates the stable dispersion of the above composition or lowers the mechanical properties of the final black matrix.

The solvent serves to dissolve the black photosensitive resin composition of the present invention. The action of the component, if the solvent is usually used for the black photosensitive resin composition, there is no limitation on the source thereof. Preferred are ethers, aromatic hydrocarbons, ketones, alcohols, esters or decylamines.

Specific examples of the solvent include: ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; propylene glycol monoalkyl ether such as propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; diethylene glycol dialkyl ether, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether , diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetate, such as methyl cellosolve acetate, ethyl cellosolve acetate; alkylene glycol alkyl ether acetate, Such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate; aromatic hydrocarbons such as benzene , toluene, xylene, mesitylene; ketones, such as methyl ethyl ketone, acetone, methyl n-amyl ketone, methyl isobutyl ketone, cyclohexanone; alcohols, such as ethanol, propanol, butanol, Hexanol, cyclohexanol, ethylene glycol, glycerol; esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone .

In view of applicability and dryness, an organic solvent having a boiling point of 100 to 200 ° C is preferred. For example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate Used alone or in combination.

The solvent is used in an amount to form a 100% by weight of the black photosensitive resin composition, and may usually be 20 to 85% by weight. Within this range, the solvent can To ensure that the above composition has good applicability.

Further, the black photosensitive resin composition according to the present invention may include at least one additive selected from the group consisting of a adhesion promoter, a surfactant, a dispersant, an antioxidant, a UV absorber, a heat resistant polymerization agent, and a leveling agent. .

The adhesion promoter may be selected from the group consisting of methacryloxypropyltrimethoxydecane, methacryloxypropyldimethoxydecane, methacryloxypropyltriethoxydecane and At least one methacryl decyl decane coupling agent in the group consisting of acryloxypropyl dimethoxy decane; or selected from the group consisting of octyltrimethoxydecane, dodecyltrimethoxydecane, and octadecene At least one alkyltrimethoxydecane in the group consisting of alkyltrimethoxydecane.

Examples of surfactants useful in the present invention include, but are not limited to, MCF 350SF, F-475, F-488, and F-552 (DIC).

Dispersants and leveling agents which are typical in the art can be used in the present invention.

Examples of antioxidants are 2,2-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butylphenol (2,6-g, t-butylphenol); UV absorbers Examples are 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chloro-benzotriazole and alkoxybenzophenone; and examples of heat-resistant polymerization agents are Hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4-thiobis(3-methyl-6-tert Butylphenol), 2,2-methylenebis(4-methyl-6-tert-butylphenol) and 2-mercaptoimidazole.

The photosensitive resin composition of the present invention may further include a second additive selected from the group consisting of a carbon black dispersant, a resin binder having a functionality, a monomer, a radiosensitive compound, and a combination thereof.

Another aspect of the present invention provides a black matrix prepared from the above black photosensitive resin composition, and an image display device including the black matrix.

The preparation of the above black photosensitive resin composition is not particularly limited, but can be obtained in a conventional manner.

The black matrix can be introduced by patterning the film lithography. In this regard, the photolithography method is not particularly limited, and any method usable with the photosensitive resin composition can be utilized.

For example, a patterned black matrix can be obtained by: a) coating a black photosensitive composition on the surface of the substrate; b) pre-curing the solvent to dryness (prebaking); c) masking the coating in the light Exposure is performed in the presence of a mold to selectively cure the coating in the exposed areas; d) to dissolve the unexposed areas with an alkali soluble solution to form a pattern; and e) to dry and post-bake the pattern.

The substrate may be a glass substrate or a polymer substrate. Preferably, the glass substrate can be made of the following materials: soda lime glass, containing bismuth. Bismuth glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass or quartz. The polymer substrate can be made of polycarbonate, acryl, polyethylene terephthalate, polyether sulfide or polyfluorene.

The coating step may be performed in a wet coating manner using a coating device such as a roll coater, a spin coater, a slit spin coater, a slit coater (die coater), an inkjet printer, or the like. .

For the pre-baking step, use an oven or hot plate. In the pre-baking step, The heating temperature and time are appropriately selected depending on the solvent used. For example, prebaking can be carried out at 80 to 150 ° C for 1 to 30 minutes.

After prebaking, exposure was performed using a stepper. In this regard, a photomask is placed over the coating to selectively expose only regions corresponding to the desired pattern. Visible light, UV light, X-rays, and electron beams can be used.

After the exposure, the unexposed regions are removed by alkaline development to form a desired pattern. The alkaline developer suitable for alkaline development may be, for example, an alkali metal or alkaline earth metal carbonate solution. In particular, in a developing machine or an ultrasonic cleaner, an alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate or lithium carbonate can be used at 10 to 50 ° C, preferably at 20 to 40 ° C.

In order to enhance the adhesion between the pattern covering conversion layer and the substrate, post-baking is performed at 80 to 220 ° C for 10 to 120 minutes. Similar to prebaking, post-baking can utilize an oven or hot plate.

In such a process, the thickness of the black matrix is controlled to be 1 micrometer to several thousands micrometers, preferably 0.1 to 100 μm, and more preferably 1 to 50 μm.

The image display device mounted with the black matrix according to the present invention may include, but is not limited to, a liquid crystal display, an OLED, and a flexible display.

The following examples are provided to provide a better understanding of the invention, and are not intended to limit the invention.

Synthesis Example 1: Synthesis of Card Multi-Binder Resin (A-1)

In a 500 ml four-necked flask, 231 g of bisphenolphthalein type epoxy resin (231 epoxy equivalent), 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-diisobutyl group were mixed. Phenol and 72.0 g of acrylic acid were then dissolved at 90 to 100 ° C while supplying air thereto at a rate of 25 ml / minute. As the mixture is heated at this temperature, the mixture gradually turns into a white turbid solution. Then, the heating temperature was gradually raised to 120 ° C to complete the dissolution. The resulting solution was clear and viscous. The solution was heated and stirred until the acid value measured at regular intervals was less than 2.0 mg KOH/g. It took 8 hours to reach the target acid value (0.8). Subsequently, the solution was cooled to room temperature to obtain a bisphenolphthalein type epoxy acrylate which was a colorless transparent solid. Then, 303 g of bisphenolphthalein type epoxy acrylate was dissolved in 2 kg of cellosolve acetate, and 38 g of 1,2,3,6-tetrahydrophthalic anhydride and 73.5 g of biphenyltetracarboxylic acid were slowly added. Dihydride and 1 g of tetraethylammonium bromide. After the temperature was slowly raised to 110-115 ° C, the reaction of 2 hours produced Resin A-1 (m/n = 5/5). The reactants of the anhydride were identified by IR spectroscopy. The obtained resin A-1 had an intrinsic viscosity of 0.2 dl/g (?nh = 0.2).

Synthesis Example 2: Synthesis of Card Multi-Binder Resin (A-2)

2 kg of cellosolve acetate was added to 303 g of the bisphenolphthalein type epoxy acrylate obtained in Synthesis Example 1, and the resulting solution was 38 g of 1,2,3,6-tetrahydrophthalic anhydride, 80.5 g. The benzophenone tetracarboxylic dianhydride was mixed with 1 g of tetraethylammonium bromide. After the temperature was slowly raised to 110-115 ° C, the reaction of 2 hours produced Resin A-2 (m/n = 5/5). The reactants of the anhydride were identified by IR spectroscopy. The obtained resin A-2 had an intrinsic viscosity of 0.3 dl/g (?nh = 0.3).

Synthesis Example 3: Synthesis of Acrylate Binder Resin (A-3)

200 ml of propylene glycol monomethyl ether acetate and 1.5 g of azobisisobutyronitrile were placed in a 500 ml polymerization vessel, and methacrylic acid, methyl group in a molar ratio of 20:20:40:20 was added in an amount of 40% by weight. Glycidyl acrylate, methyl A mixture of acrylate monomers of methyl acrylate and dicyclopentanyl acrylate. The mixture was polymerized at 70 ° C for 5 hours under a nitrogen atmosphere with stirring to obtain an acrylate-based polymer resin A-3. The obtained copolymer had a weight average molecular weight of 25,000 and a degree of dispersion of 2.0 by measurement.

Synthesis Example 4: Synthesis of Photopolymerization Initiator (C-1) Reaction 1

6.31 g of anhydrous aluminum chloride was added to a solution of 5.0 g of 2-nitroguanidine in 100 ml of anhydrous nitrobenzene, followed by heating to 45 °C. A solution of 2.79 g of acetamidine chloride in 30 ml of anhydrous nitrobenzene was slowly added over 30 minutes, and the reaction was heated to 65 ° C and stirred for 1 hour. Then, the reaction mixture was cooled to room temperature, 70 ml of distilled water was added and stirred for 30 min, and then the product was filtered. The solid product was dispersed in 50 ml of diethyl ether, stirred at room temperature for 30 min, filtered and dried to give the compound 1 (1-(9,9-di-H-7-nitrofluorenone-2) as a pale yellow solid. -yl)-ethanone). 5.08g.

Reaction 2

0.49 g of hydroxylamine HCl and 0.58 g of sodium acetate were added to a dispersion of 1.5 g of reactant 1 in 30 ml of ethanol, and the resulting solution was gradually heated under reflux for 2 hours. The reaction mixture was cooled to room temperature, 20 ml of distilled water was added, and stirred for 30 min to give a precipitate. It was filtered, washed several times with distilled water, and dried to give the compound 2 (1-(9,9-H-7-nitroindol-2-yl)-ethanone oxime) as a light gray solid. 1.38g.

Reaction 3

0.69 g of acetic anhydride was added to a dispersion of 1.20 g of the reactant 2 in 50 mL of ethyl acetate, and the resulting solution was gradually heated under reflux for 3 hours. Time. The reaction mixture was cooled to room temperature, and washed sequentially with 20 ml of saturated aqueous sodium hydrogen carbonate and 20 ml of distilled water. The organic layer thus obtained was dried over anhydrous magnesium sulfate and solvent was evaporated from vacuo. The residue was recrystallized from 20 mL of MeOH to give the title compound C-1 (1-(9,9-H-7-nitroindol-2-yl)-ethanone oxime-O- as a pale yellow solid. Acetate). 1.22g.

Synthesis Example 5: Synthesis of Photopolymerization Initiator (C-2) Reaction 1

Under a nitrogen atmosphere, 200.0 g of hydrazine, 268.8 g of potassium hydroxide and 19.9 g of potassium iodide were dissolved in 1 L of anhydrous dimethyl hydrazine. The solution was maintained at 15 ° C, and 283.3 g of ethyl bromide was slowly added over 2 hours, followed by stirring at 15 ° C for 1 hour. Then, the reaction mixture was mixed with 2 L of distilled water by stirring for 30 minutes, and extracted with 2 L of dichloromethane. The extracted organic layer was washed twice with 2 L of distilled water and dried over anhydrous magnesium sulfate. After the distillation solvent was removed by vacuum, the residue was fractionated in vacuo to give the material 1 (9,9-diethyl-9H-indole) as a highly viscous pale yellow liquid. 248.6g.

Reaction 2

A solution of 100.5 g of Reagent 1 in 1 L of dichloromethane was cooled to -5 °C and 72.3 g of aluminum chloride was slowly added. Then, 50.1 g of a propylene chloride dilution in 50 ml of dichloromethane was slowly added over 2 hours, and care was taken not to raise the temperature of the reaction mixture, followed by stirring at -5 ° C for 1 hour. The reaction mixture was slowly poured into 1 L of ice water and stirred for 30 min. The organic layer thus separated was washed with 500 ml of distilled water and distilled in vacuo. The residue was purified by silica gel column chromatography (eluent: ethyl acetate:hexanehexanesssssssssssssssssssssssssssss -芴 -2-yl)-1-propanone). 75.8g.

Reaction 3

150 ml of 4N hydrochloric acid and 24.7 g of iso nitrite in 1,4-dioxane were added in sequence to a solution of 44.5 g of reactant 2 in 900 ml of tetrahydrofuran (THF), followed by 25 ° C Stir for 6 hours. The reaction mixture was mixed with 500 ml of ethyl acetate for 30 minutes by stirring, and the organic layer thus formed was washed with 600 mL of distilled water and dried over anhydrous magnesium sulfate. After the solvent was removed by vacuum distillation, the residue was crystallised from ethyl acetate:hexane (1:6) -9H-indol-2-yl)-1,1-2propanedione-2-indole). 27.5g.

Reaction 4

A solution of the reactant 3 in 1 L of N-methyl-2-pyrrolidone (NMP) was kept at -5 ° C, 35.4 g of triethylamine was added, and stirred for 30 min. A solution of 27.5 g of acetamidine in 75 mL of N-methyl-2-pyrrolidone was slowly added, and care was taken not to raise the temperature of the reaction mixture, followed by stirring for 30 minutes. 1 L of distilled water was slowly added to the reaction mixture and stirred for 30 minutes. The organic layer thus formed was dried over anhydrous magnesium sulfate. After removing the solvent by vacuum distillation, the residue was recrystallized from 1 L of ethanol and dried to give the solvent C-2 (1-(9,9-diethyl-9H-indole-2-) as a light gray solid. Base)-1,2-propanedione-2-indole-O-acetate). 93.7g.

Examples 1 to 12 and Comparative Examples 1 to 5: Preparation of a black photosensitive resin composition

A black photosensitive resin composition was prepared using the ingredients and contents (unit: % by weight) shown in Table 1 below.

Test Example 1: Evaluation (1) Adhesion to the substrate

The photosensitive resin compositions of the examples and the comparative examples were placed on a glass substrate A layer was formed and dried on a hot plate at 100 ° C for 1 min to form a film. These films were covered with a patterned photomask and then exposed to a high pressure mercury lamp emitting a wavelength of 365 nm, wherein the pattern thickness of the patterned photomask was varied from 1 [mu]m to 20 [mu]m at 1 [mu]m intervals. Thereafter, the exposed film was post-baked in a convection oven at 230 ° C for 100 minutes, and subjected to PCT (pressure cooker test) to be evaluated using an orthogonal test (PCT conditions: 2 atm, humidity 120%, 4 hours / 1 cycle). Layering between glass and film.

(2) Bonding during development

The photosensitive resin compositions of the examples and the comparative examples were formed into a layer having a thickness of 1 μm on a glass substrate of 1 mm thick, and dried on a hot plate at 100 ° C for 1 minute to form a film. These films were covered with a patterned photomask and then exposed to a high pressure mercury lamp emitting a wavelength of 365 nm, wherein the pattern thickness of the patterned photomask was varied from 1 [mu]m to 20 [mu]m at 1 [mu]m intervals. Thereafter, the exposed film was developed at 30 ° C under an atmospheric pressure using a 1% aqueous KOH solution. The minimum pattern of the remaining patterns is measured on the basis of the mask size.

As can be seen from Table 2, the black photosensitive resin compositions of Examples 1 to 12 exhibited excellent adhesion at the time of development, thereby remarkably reducing the size of the smallest pattern which can be formed without loss, and thus high resolution can be obtained. Color filter. Further, the patterns were found to have high durability due to their firm adhesion to the substrate.

Meanwhile, the compositions of Examples 4, 5, 9 and 10 in which a slight excess of the alkali-soluble binder resin and the photopolymerization initiator were used had a smaller minimum pattern size and a higher adhesion to the substrate than the comparative example. Sex, but has a larger minimum pattern size compared to other embodiments.

The composition using the acrylate-based binder resin of Comparative Example 1 was observed to exhibit high adhesion to the substrate, but the adhesion was lowered during development.

Further, it was observed that the compositions of Comparative Examples 2 and 3 in which a conventional triazine-based initiator was used in place of the oxime ester-based initiator of the present invention exhibited a decrease in adhesion at the time of development and adhesion to a substrate.

Claims (3)

A black photosensitive resin composition comprising: an alkali-soluble binder resin, a photopolymerizable compound, a photopolymerization initiator, a black pigment, and a solvent, wherein the alkali-soluble binder resin includes a card-type binder resin, and The photopolymerization initiator includes at least one compound represented by the following Chemical Formula 5: Wherein R ₁₄ to R ₂₃ are each independently a hydrogen atom, a halogen atom, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, 7~ An arylalkyl group of 40 carbon atoms, a hydroxyalkyl group of 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group of 2 to 40 carbon atoms or a cycloalkyl group of 3 to 20 carbon atoms, and wherein the black The photosensitive resin composition includes an alkali-soluble binder resin in an amount of 1 to 40% by weight, a photopolymerizable compound in an amount of 1 to 20% by weight, a photopolymerization initiator in an amount of 0.1 to 12% by weight, and a content of 5 ~20% by weight of black pigment and a certain amount of solvent to form 100% by weight. A black matrix prepared from the black photosensitive resin composition as described in claim 1. An image display apparatus comprising the black matrix as claimed in claim 2.