KR20160109444A - A colored photo sensitive resin composition, color filter and liquid crystal display device having the same - Google Patents

Abstract

The present invention relates to a blue photosensitive resin composition, a color filter and a liquid crystal display device comprising the same. The blue photosensitive resin composition does not generate peeling due to excellent adhesion and can improve liquid crystal bubbles by using a fluorene oxime ester derivative compound as a photopolymerizable initiator in a blue pigment. In addition, the color filter and the liquid crystal display device produced by using the blue photosensitive resin composition can improve reliability because there is no loss of patterns.

Description

TECHNICAL FIELD [0001] The present invention relates to a blue light-sensitive resin composition, a color filter, and a liquid crystal display device including the same.

The present invention relates to a blue photosensitive resin composition, a color filter, and a liquid crystal display including the same.

BACKGROUND ART [0002] Color filters are widely used in imaging devices, liquid crystal display devices, and the like, and their application range is rapidly expanding. A color filter used for a color liquid crystal display device, an image pickup device, or the like is generally formed by uniformly applying a colored photosensitive resin composition containing a colorant corresponding to red, green and blue colors on a substrate on which a black matrix is patterned by spin coating (Hereinafter also referred to as "post-baking") is repeated for each color so as to obtain a pixel of each color As shown in FIG.

As such a colored photosensitive resin composition, a photosensitive resin composition containing an alkali soluble binder resin, a photopolymerizable compound, a photopolymerization initiator, a pigment solvent, and a black pigment in the formation of a black matrix is used.

Particularly, among the photosensitive resin compositions, the blue pigment has a short wavelength (about 400 nm in the second half) region, unlike the other color pigments, and the toxic adhesion is deteriorated in a high temperature and high humidity environment.

Recently, an example of using an oxime ester fluorene derivative compound as a photopolymerization initiator to achieve low exposure and high sensitivity has been disclosed, but this does not solve the problem that deterioration of the quality of a liquid crystal display device occurs due to peeling of a color filter in a blue pigment Respectively.

Korean Patent Laid-Open No. 10-2013-0124215 (published on Mar. 13, 2013) discloses a novel oxime ester fluorene compound, a photopolymerization initiator containing the same, and a photoresist composition. The above-mentioned prior art provides a photoresist composition which uses oxime ester fluorene derivative compound as a photopolymerization initiator and has a sensitivity higher than that of the oxime ester fluorene derivative compound.

Korean Patent No. 10-1435652 (registered Aug. 22, 2014) relates to a novel? -Oxime ester fluorene compound, a photopolymerization initiator containing the same, and a photoresist composition. The above-mentioned prior arts provide a photoresist composition excellent in physical properties such as pattern stability, chemical resistance and ductility, by using a? -Oxime ester fluorene derivative compound as a photopolymerization initiator and having a sensitivity higher than that of using the? -Oxime ester fluorene derivative compound.

The prior arts have a high sensitivity effect only by using oxime ester fluorene compound as a photopolymerization initiator and there is no technology market for using it with a specific blue pigment. In the high temperature and high humidity environment, the adhesion of the color filter is lowered, The quality of the liquid crystal display device is deteriorated.

Korean Patent Publication No. 10-2013-0124215 Korean Patent No. 10-1435652

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a blue photosensitive resin composition which is excellent in adhesion and does not cause peeling, And a liquid crystal display device including the same.

In order to achieve the above object, the blue photosensitive resin composition according to an embodiment of the present invention includes a photopolymerization initiator and a colorant, and the photopolymerization initiator includes at least one oxime ester fluorene derivative compound represented by the following formula .

[Chemical Formula 1]

 (In the formula 1,

Each of R ₁ to R ₃ is independently selected from the group consisting of hydrogen, a halogen group, a C1 to C20 alkyl group, a C6 to C20 aryl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, A C1 to C20 hydroxyalkyl group, a C1 to C20 hydroxyalkoxy group, a C1 to C20 alkyl group or a C3 to C20 cycloalkyl group;

R ₄ to R ₁₀ are independently selected from the group consisting of hydrogen, a C 1 to C 20 alkyl group, a C 6 to C 20 aryl group, a C 1 to C 20 alkoxy group, a C 6 to C 20 aryl group, a C to C 20 alkyl group, a C to C 20 hydroxyalkyl group, A hydroxyalkoxy group of-C20, a C1-C20 alkyl group or a C3-C20 cycloalkyl group, amino, nitro, cyano or hydroxy;

n is 0 or 1.)

As described above, the blue photosensitive resin composition according to the present invention is excellent in adhesion strength and does not cause peeling and can improve liquid crystal bubble phenomenon by using oxime ester fluorene derivative compound as a photopolymerization initiator for blue pigments.

Further, the color filter and the liquid crystal display device manufactured using the blue photosensitive resin composition of the present invention can improve the reliability because there is no loss of pattern.

The blue photosensitive resin composition according to the present invention comprises a photopolymerization initiator and a colorant, and may further comprise an alkali-soluble binder resin, a photopolymerizable compound and a solvent.

The photopolymerization initiator contained in the blue photosensitive resin composition of the present invention may be an oxime ester fluorene derivative compound represented by the following formula (1).

[Chemical Formula 1]

(In the formula 1,

Each of R ₁ to R ₃ is independently selected from the group consisting of hydrogen, a halogen group, a C1 to C20 alkyl group, a C6 to C20 aryl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, A C1 to C20 hydroxyalkyl group, a C1 to C20 hydroxyalkoxy group, a C1 to C20 alkyl group or a C3 to C20 cycloalkyl group;

R ₄ to R ₁₀ are independently selected from the group consisting of hydrogen, a C 1 to C 20 alkyl group, a C 6 to C 20 aryl group, a C 1 to C 20 alkoxy group, a C 6 to C 20 aryl group, a C to C 20 alkyl group, a C to C 20 hydroxyalkyl group, A hydroxyalkoxy group of-C20, a C1-C20 alkyl group or a C3-C20 cycloalkyl group, amino, nitro, cyano or hydroxy;

n is 0 or 1.)

Halogen mentioned in the present invention is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

The alkyl group referred to in the present invention includes straight or branched one, and examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, -Octyl, n-decyl, and the like.

Cycloalkyl groups mentioned in the present invention include cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, adamantyl, and substituted and unsubstituted boronyl, norbornyl and norbornenyl, and the like.

The aryl groups mentioned in the present invention include phenyl, biphenyl, terphenyl, stilbenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl and the like.

The alkoxy group referred to in the present invention includes straight chain or branched and includes, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, isobutoxy, And the like.

In this case, the photopolymerization initiator may have n of 1 or 2, and when n is 0, it may be represented by the following general formula (2), and when n is 1, the following general formula (3)

 (2)

(In the formula (2)

R ₁₁ to R ₁₃ are each independently selected from the group consisting of hydrogen, a halogen group, a C1 to C20 alkyl group, a C6 to C20 aryl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, A C1 to C20 hydroxyalkyl group, a C1 to C20 hydroxyalkoxy group, a C1 to C20 alkyl group or a C3 to C20 cycloalkyl group;

A represents hydrogen, a C1 to C20 alkyl group, a C6 to C20 aryl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C1 to C20 alkyl group, a C1 to C20 hydroxyalkyl group, A C1-C20 alkyl group or a C3-C20 cycloalkyl group, amino, nitro, cyano or hydroxy.

The substituents comprising alkyl, alkoxy and other alkyl moieties described in the present invention include both straight chain or branched forms, and the cycloalkyl includes not only a single ring system but also several cyclic hydrocarbons. The aryls described in the present invention are organic radicals derived from aromatic hydrocarbons by the removal of one hydrogen, with a single or fused ring system, suitably containing from 4 to 7, preferably 5 or 6, ring atoms in each ring And includes a form in which a plurality of aryls are connected by a single bond. Hydroxyalkyl means OH-alkyl in which a hydroxy group is bonded to an alkyl group as defined above, and hydroxyalkoxyalkyl means hydroxyalkyl-O-alkyl in which an alkoxy group is bonded to the hydroxyalkyl group.

The C1-C20 alkyl group described in the present invention is preferably a C1-C10 alkyl group, and more preferably a C1-C6 alkyl group. The C6-C20 aryl group is preferably an C6-C18 aryl group. The C1-C20 alkoxy group is preferably a C1-C10 alkoxy group, more preferably a C1-C4 alkoxy group. The C6-C20 aryl group and C1-C20 alkyl group are preferably C6-C18 aryl group and C1-C10 alkyl group, more preferably C6-C18 aryl group and C1-C6 alkyl group. The C1-C20 hydroxyalkyl group is preferably a C1-C10 hydroxyalkyl group, and more preferably a C1-C6 hydroxyalkyl group. The C1-C20 hydroxyalkoxy group and the C1-C20 alkyl group are preferably a C1-C10 hydroxyalkoxy group and a C1-C10 alkyl group, more preferably a C1-C4 hydroxyalkoxy group and C1-C6 Lt; / RTI > The C3-C20 cycloalkyl group is preferably a C3-C10 cycloalkyl group.

Specifically, each of R ₁₁ to R ₁₃ independently represents a hydrogen atom, a bromine atom, a chloro atom, a methyl group, an ethyl group, a n-propyl group, an i- propyloxy, i-propyloxy, n-pentyl, n-hexyl, i-hexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, Butoxy, i-butoxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxy n-propyl, hydroxy n-butyl, hydroxy i-butyl, hydroxy n-pentyl, , Hydroxy n-hexyl, hydroxy i-hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, Hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl; < RTI ID = 0.0 > R < / RTI >

A is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i- butyl, t- butyl, phenyl, naphthyl, biphenyl, terphenyl anthryl, indenyl, And examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, sec-butyl, Hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, amino, nitro, cyano or hydroxy, but is not limited thereto.

More specifically, R < ₁₁ > is hydrogen or n-butyl; R ₁₂ is methyl; R ₁₃ may be methyl, n-butyl or phenyl.

The oxime ester fluorene derivative compound represented by Formula 2 according to the present invention can be prepared as shown in Reaction Scheme 1 below.

[Reaction Scheme 1]

(In the above Reaction Scheme 1, R ₁₁ to R ₁₃ and A are the same as defined in Chemical Formula 2, and X is halogen.)

 (3)

(3)

R ₁₄ to R ₂₃ are each independently selected from the group consisting of hydrogen, a halogen group, a C1 to C20 alkyl group, a C6 to C20 aryl group, a C1 to C20 alkoxy group, a C7 to C40 arylalkyl group, A hydroxyalkoxyalkyl group of C2 to C40, or a cycloalkyl group of C3 to C20.

The alkyl groups described in the present invention refer to straight or branched chain hydrocarbon chain radicals consisting solely of carbon and hydrogen atoms, free of unsaturation and bonded to the remainder of the molecule by a single bond. The alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and most preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of such unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, And the like. The at least one hydrogen atom contained in the alkyl group may be substituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a thiol group (-SH), a nitro group, a cyano group, a substituted or unsubstituted amino group, an amidino group, a hydrazine group, C20 alkyl group, C1-C20 halogenated alkyl group, C1-C20 alkenyl group, C1-C20 alkynyl group, C1-C20 heteroalkyl group, C6-C20 aryl group, C6-C20 arylalkyl group , A C6-C20 heteroaryl group, or a C6-C20 heteroarylalkyl group.

The alkoxy group is preferably an oxygen-containing straight-chain or branched alkoxy group each having a C1-C20 alkyl moiety. More preferred are alkoxy groups having 1 to 10 carbon atoms and most preferred are alkoxy groups having 1 to 4 carbon atoms. Examples of such alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and t-butoxy. The alkoxy group may be further substituted with one or more halo atoms such as fluoro, chloro or bromo to provide a haloalkoxy group. Examples thereof include a fluoromethoxy group, a chloromethoxy group, a trifluoromethoxy group, a trifluoroethoxy group, a fluoroethoxy group, and a fluoropropoxy group. At least one hydrogen atom of the alkoxy group may be substituted with the same substituent as the alkyl group.

The cycloalkyl group includes not only a single ring system but also a plurality of cyclic hydrocarbons, and at least one hydrogen atom in the cycloalkyl group may be substituted with the same substituent as the alkyl group. The cycloalkyl group is preferably 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms, and most preferably a cycloalkyl group having 3 to 8 carbon atoms.

The aryl group means an aromatic monocyclic or multicyclic hydrocarbon ring system consisting solely of hydrogen and carbon, wherein the ring system may be partially or fully saturated. At least one hydrogen atom in the aryl group may be substituted with the same substituent as in the case of the alkyl group. The aryl group is an organic radical derived from aromatic hydrocarbons by one hydrogen elimination, and includes a single or fused ring system, suitably containing from 4 to 7, preferably 5 or 6, ring atoms in each ring , And a form in which a plurality of aryls are connected by a single bond. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 18 carbon atoms.

The hydroxyalkyl group means an OH-alkyl group in which a hydroxy group is bonded to the alkyl group defined above, and the hydroxyalkoxyalkyl group means hydroxyalkyl-O-alkyl in which the hydroxyalkyl group and the alkyl group are connected by oxygen. The hydroxyalkyl group is preferably C1 to C20, more preferably C1 to C10, and most preferably C1 to C6. 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.

The arylalkyl group means that at least one hydrogen atom of the alkyl group is substituted with the 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.

More specifically, R ₁₄ to R ₂₃ each independently represents a group selected from the group consisting of hydrogen, bromo, chloro, iodo, methyl, ethyl, n-propyl, i- A naphthyl group, an naphthyl group, a biphenyl group, a terphenyl group, an anthryl group, an indenyl group, a phenanthryl group, a methoxy group, an ethoxy group, a n-propyl group, a n-propyl group, a n-propyl group, a n-propyl group, a n-butoxy group, Butyl group, a hydroxy i-butyl group, a hydroxy n-pentyl group, a hydroxy i-pentyl group, a hydroxy n-hexyl group, a hydroxy i-hexyl group, a hydroxymethoxymethyl group, a hydroxymethoxyethyl group, A propyl group, a propyl group, a hydroxymethoxybutyl group, a hydroxyethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, a hydroxyethoxypentyl group Or a hydroxyethoxyhexyl group.

More specifically, R ₁₄ is hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group; R ₁₅ is a methyl group, an ethyl group, or a propyl group; R ₁₆ is a methyl group, an ethyl group, a propyl group, or a butyl group; R ₁₇ to R ₂₃ may be hydrogen.

The oxime ester fluorene derivative represented by Formula 3 according to the present invention can be prepared as shown in Reaction Scheme 2 below.

[Reaction Scheme 2]

(Wherein R ₁₄ to R ₂₃ and A are each independently selected from the group consisting of hydrogen, halogen, C 1 to C 20 alkyl, C 6 to C 20 aryl, C 1 to C 20 alkoxy, C 7 to C 40 arylalkyl, C20 hydroxyalkoxy group, C2-C40 hydroxyalkoxyalkyl group or C3-C20 cycloalkyl group, and X is halogen.

The photopolymerization initiator is contained in an amount of 0.1 to 10% by weight based on the total weight of the solid content in the blue photosensitive resin composition of the present invention. When the photopolymerization initiator is contained within the above range, the blue photosensitive resin composition becomes highly sensitive, so that the strength of the pixel portion formed using the composition and the smoothness of the surface of the pixel portion tends to be favorable.

The colorant contained in the blue photosensitive resin composition of the present invention may be an organic pigment, which is a compound classified as a pigment in the color index (published by The Society of Dyers and Colourists), or a metal oxide, a metal complex salt, an inorganic salt of barium sulfate And organic pigments are more preferable because they are excellent in heat resistance and color development.

Specific examples of the colorant include C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 60, and the like.

Further, the colorant may be C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Violet pigments such as Pigment Violet 38, and the like.

The coloring agent may be contained in an amount of 5 to 40% by weight based on the solid content in the blue photosensitive resin composition. If the coloring agent is contained in the above range, the color density of the pixel is sufficient even when a thin film is formed, The residue is not generated since it is not degraded.

At this time, the pigment dispersion containing the pigment dispersant is subjected to the dispersion treatment, whereby the pigment dispersion in which the blue pigment is uniformly dispersed in the solution can be obtained. Examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, polyamines surfactants, and polyacrylic surfactants. These surfactants may be used singly or in combination of two or more. Can be used.

The alkali-soluble binder resin contained in the blue photosensitive resin composition of the present invention is prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to have solubility in an alkali developing solution used in a developing process used for forming a pattern do. In order to ensure compatibility with the dye and storage stability of the blue photosensitive resin composition, the acid value of the alkali-soluble binder resin is preferably 30 to 150 mgKOH / g. When the acid value of the alkali-soluble binder resin is less than 30 mgKOH / g, it is difficult to secure a sufficient developing rate of the blue photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, There is a problem in that the dye in the blue photosensitive resin composition is precipitated or the storage stability of the blue photosensitive resin composition is lowered and the viscosity tends to rise.

A hydroxyl group may be added to secure further developability of the alkali-soluble binder resin. The developing rate for imparting hydroxyl groups is improved, but the sum of the hydroxyl value of the alkali-soluble binder resin and the photopolymerizable compound is limited to 50 mgKOH / g or more and 250 mgKOH / g or less. When the sum of the hydroxyl groups is less than 50 mgKOH / g, a sufficient developing rate can not be secured. When it exceeds 250 mgKOH / g, the dimensional stability of the formed pattern is lowered and the linearity of the pattern becomes poor and the compatibility with the dye is deteriorated A problem of storage stability tends to occur.

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids; (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferable.

In order to impart a hydroxyl group to the alkali-soluble binder resin, an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group can be copolymerized, and a compound having a glycidyl group in a copolymer of an ethylenically unsaturated monomer having a carboxyl group ≪ / RTI > And further by reacting a copolymer of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group with a compound having a glycidyl group.

Specific examples of the butylenes unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylamide and the like, and 2-hydroxyethyl (meth) acrylate is preferable, and two or more kinds thereof can be used in combination.

Specific examples of the glycidyl group-containing compounds include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, Benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, aryl glycidyl ether, glycidyl methacrylate, glycidyl glycidyl ether, Epoxycyclohexanecarboxylic acid, epoxycyclohexanecarboxylic acid, epoxycyclohexanedicarboxylic acid, epoxycyclohexanedicarboxylic acid, epoxycyclohexanedicarboxylic acid, epoxycyclohexanedicarboxylic acid, epoxycyclohexanone,

The unsaturated monomers copolymerizable in the preparation of the alkali-soluble binder resin are exemplified below, but are not limited thereto.

Specific examples of the polymerizable monomer having an unsaturated bond capable of copolymerization include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, Aromatic vinyl compounds such as methyl ether, m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0.2.6] decan- Alicyclic (meth) acrylates such as chloropentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds.

These unsaturated monomers may be used alone or in combination of two or more.

The content of the alkali-soluble binder resin should satisfy the condition that the sum of the hydroxyl value of the alkali-soluble binder resin and the photopolymerizable compound is from 50 mgKOH / g to 250 mgKOH / g. The content of the alkali- By weight, more preferably 10 to 30% by weight. When the content of the alkali-soluble resin is within the above range, solubility in a developing solution is sufficient, pattern formation is easy, reduction of film in the pixel portion of the exposed portion is prevented at the time of development, Do.

The photopolymerizable compound contained in the blue photosensitive resin composition of the present invention is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money, and the like, but are not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, but are not limited thereto.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (metha) acrylate, propoxylated dipentaerythritol hexa Acrylate or dipentaerythritol hexa (meth) acrylate, but are not limited thereto.

Of the photopolymerizable compounds exemplified above, bifunctional or higher functional polyfunctional monomers can be preferably used. The above-mentioned photopolymerizable compounds may be used alone or in combination of two or more.

The photopolymerizable compound may be contained in an amount of 1 to 20% by weight based on the solid content in the blue photosensitive resin composition. When the photopolymerizable compound is contained in the above range, the strength and smoothness of the pixel portion are preferably improved.

The solvent contained in the blue photosensitive resin composition of the present invention is not particularly limited, and various solvents used in the art can be used.

Specific examples of the solvent 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 dimethyl ether, diethylene glycol diethyl ether, di Diethylene glycol dialkyl ethers such as ethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, Alkylene glycol alkyl ether acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, Ketones, Ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, ethyl 3-ethoxypropionate, Esters such as methyl methoxypropionate, and cyclic esters such as? -Butyrolactone.

In view of the coating property and the drying surface in the solvent, a solvent having a boiling point of 100 to 200 DEG C may be preferably used. More preferred examples thereof include alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, Methoxypropionate, and methyl 3-methoxypropionate. More preferred are esters such as propylene glycol monomethyl ether acetate, ropylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Methyl and the like can be used. These solvents may be used alone or in combination of two or more.

The content of the solvent is preferably 20 to 85% by weight, more preferably 50 to 80% by weight based on the total amount of the blue photosensitive resin composition. When the content of the solvent is within the above range, when the solvent is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater, or an ink jet, the application property becomes good.

The blue photosensitive resin composition of the present invention may further include an additive.

The additive is optionally added according to need. Specific examples thereof include fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents.

Specific examples of the filler include glass, silica and alumina.

Specific examples of the other polymer compound include a curable resin such as epoxy resin and maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane and the like .

As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric surfactants. These may be used alone or in combination of two or more. Specific examples of the above surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty phase esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes, (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), , MEGAFAC (manufactured by Dainippon Ink and Chemicals, Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.) SOLSPERSE (manufactured by Genene), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 (aminoethyl) - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Trimethoxysilane, and the like.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone. Specific examples of the anti-aggregation agent include sodium polyacrylate.

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

The present invention also provides a color filter made of the blue photosensitive resin composition.

When the color filter of the present invention is applied to an image display apparatus, since it emits light by the light of the display apparatus light source, it is possible to realize more excellent light efficiency. In addition, since color light is emitted, color reproducibility is better and light is emitted in all directions due to the optical luminescence, so that the viewing angle is improved and the luminance characteristic is excellent.

The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be a substrate of the color filter itself, or may be a portion where the color filter is placed on a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiO _x ), or a polymer substrate. The polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer may be a layer containing the photosensitive resin composition of the present invention, and may be a layer formed by applying the photosensitive resin composition and exposing, developing, and curing the composition in a predetermined pattern.

The pattern layer formed of the colored photosensitive resin composition may have a red pattern layer containing the red quantum dot particles, a green pattern layer containing the green quantum dot particles, and a blue pattern layer containing the blue quantum dot particles. During the light irradiation, the red pattern layer emits red light, the green pattern layer emits green light, and the blue pattern layer emits blue light.

In such a case, the emitted light of the light source is not particularly limited when applied to an image display apparatus, but a light source that emits blue light preferably in terms of better luminance and color reproducibility can be used.

According to another embodiment of the present invention, the pattern layer further includes a red pattern layer, a green pattern layer, and a transparent pattern layer not containing the quantum dot particles. In the case where only the pattern layer of two colors is provided, a light source that emits light having a wavelength that represents the remaining color that is not included can be used. For example, when a red pattern layer and a green pattern layer are included, a light source that emits blue light can be used. In such a case, red quantum dot particles emit red light and rust quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is and exhibits blue color.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between the respective patterns, and may further include a black matrix. Further, it may further comprise a protective film formed on the pattern layer of the color filter.

By including the blue pigment in the color filter, it is possible to prevent the problem that peeling may occur in the substrate and the pattern layer in a high temperature and high humidity environment.

In addition, the present invention provides a liquid crystal display device including a color filter made of the blue photosensitive resin composition. Therefore, the adhesion of the color filter can be increased, and the problem of quality deterioration of the liquid crystal display device can be prevented.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Synthetic example  One. Light curing Initiator  C-1: 1- (9,9-H-7- Nitroplorene -2 days)- Ethanone Oxime Preparation of -O-acetate

Reaction 1. 1- (9,9-H-7-Nitroploren-2-yl) -ethanone Synthesis

5.0 g (23.7 mmol) of 2-nitropluorene (1) was dissolved in 100 ml of anhydrous nitrobenzene, 6.31 g (47.4 mmol) of anhydrous aluminum chloride was added and the reaction was warmed to 45 캜 to obtain 2.79 g ) In 30 ml of anhydrous nitrobenzene was added slowly over 30 minutes, and the reaction was heated to 65 ° C and stirred for 1 hour. Then, the reaction product was cooled to room temperature, 70 ml of distilled water was added thereto, stirred for about 30 minutes, and the product was filtered. The obtained solid product was dispersed in 50 ml of ether and stirred at room temperature for 30 minutes, followed by filtration and drying to obtain 5.08 g of 1- (9,9-H-7-nitrofluoren-2-yl) (84.7%).

Reaction 2. 1- (9,9-H-7-Nitroploren-2-yl) -ethanone oxime Synthesis

1.5 g (5.92 mmol) of 1- (9,9-H-7-nitrofluoren-2-yl) -ethanone (2) were dispersed in 30 ml of ethanol, 0.49 g (7.1 mmol) of hydrochloric acid hydroxylamine, 0.58 g (7.1 mmol) of sodium was added, and then the reaction solution was gradually heated and refluxed for 2 hours. The reaction product was cooled to room temperature, and 20 ml of distilled water was added thereto. The mixture was stirred for about 30 minutes, and the resulting solid product was filtered, washed several times with distilled water and dried to obtain light gray 1- (9,9- 2-yl) -ethanone oxime (3) (1.38 g, 86.8%).

Reaction 3. 1- (9,9-H-7-Nitroploren-2-yl) -ethanone oxime-O-

1.20 g (4.47 mmol) of 1- (9,9-H-7-nitropluoren-2-yl) -ethanone oxime (3) were dispersed in 50 ml of ethyl acetate, and 0.69 g (6.76 mmol) Then, the reaction solution was gradually heated and refluxed for 3 hours. The reaction mixture was cooled to room temperature, washed with 20 ml of a saturated aqueous sodium hydrogencarbonate solution and then with 20 ml of distilled water. The recovered organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The product was recrystallized from methanol (20 ml) (87.9%) of (9,9-H-7-nitrofluoren-2-yl) -ethanone oxime-O-acetate (4).

Synthetic example  2. Light curing Initiator  C-2: 1- (9,9- Diethyl -9H- Fluorene Yl) -1,2- Propanedione -2- Oxime Preparation of -O-acetate

Reaction 1. Synthesis of 9,9-diethyl-9H-fluorene (2)

(1.80mol) of fluorene (1), 268.8g (4.80mol) of potassium hydroxide and 19.9g (0.12mol) of potassium iodide were dissolved in 1L of anhydrous dimethylsulfoxide under a nitrogen atmosphere, the reaction was maintained at 15 占 폚, 283.3 g (2.60 mol) of bromoethane was slowly added over 2 hours, and the reaction was stirred at 15 ° C for 1 hour. Then, 2 L of distilled water was added to the reaction mixture, stirred for 30 minutes, and the product was extracted with 2 L of dichloromethane. The extracted organic layer was washed twice with 2 L of distilled water, and the recovered organic layer was dried over anhydrous magnesium sulfate. The resulting product was fractionally distilled under reduced pressure to obtain 248.6 g (93.3%) of light yellow 9,9-diethyl-9H-fluorene (2) as a liquid having a high viscosity.

Reaction 2. Synthesis of 1- (9,9-diethyl-9H-fluoren-2-yl) -1-propanone (3)

After dissolving 100.5 g (0.45 mol) of 9,9-diethyl-9H-fluorene (2) in 1 L of dichloromethane, the reaction was cooled to -5 DEG C and then 72.3 g (0.54 mol) While taking care not to raise the temperature of the reaction product, 50.1 g (0.54 mol) of propionyl chloride diluted in 50 ml of dichloromethane was slowly added over 2 hours, and the reaction product was stirred at -5 ° C for 1 hour. Then, the reaction mixture was poured slowly into 1 L of ice water and stirred for 30 minutes. The organic layer was separated, washed with 500 ml of distilled water, and the recovered organic layer was distilled under reduced pressure. The resulting product was purified by silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1: 4) to obtain 75.8 g (60.6%) of light yellow solid 1- (9,9-diethyl-9H- fluoren-2-yl) -1-propanone (3).

Reaction 3. Synthesis of 1- (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione-2-oxime (4)

44.5 g (0.16 mol) of 1- (9,9-diethyl-9H-fluoren-2-yl) -1-propanone (3) was dissolved in 900 ml of tetrahydrofuran (THF) , And 24.7 g (0.24 mol) of isobutyl nitrite were added in this order, and the reaction was stirred at 25 ° C for 6 hours. Then, 500 ml of ethyl acetate was added to the reaction solution and stirred for 30 minutes. The organic layer was separated and washed with 600 ml of distilled water. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid product was dissolved in ethyl acetate: (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione-2-oxime (1, 6) as a light gray solid was obtained by recrystallization using 300 ml of a mixed solvent of (4) (27.5 g, 56.0%).

Reaction 4. Synthesis of 1- (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione-2-oxime-

(0.29 mol) of 1- (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione- (0.35 mol) of triethylamine was added to the reaction solution, and the reaction solution was stirred for 30 minutes. 27.5 g (0.35 mol) of acetyl chloride was dissolved in N -Methyl-2-pyrrolidinone was slowly added over 30 minutes, and the mixture was stirred for 30 minutes while taking care not to raise the temperature of the reaction product. Then, 1 L of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid product was recrystallized using 1 L of ethanol and then dried to obtain a pale-gray solid 1- (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione- 93.7 g (92.6%) of O-acetate (5) was obtained.

Example  1 to 4 and Comparative Examples 1 to 3

In Examples 1 to 4 and Comparative Examples 1 to 3, a solvent was added to a mixer, and an alkali-soluble binder resin, a photopolymerizable compound, a photopolymerization initiator and a colorant were added to the mixture, and the mixture was uniformly mixed with stirring to prepare a blue photosensitive resin composition Respectively. At this time, the composition of the composition is as shown in Table 1 below.

division
(weight%) Alkali soluble binder resin Photopolymerizable compound Photopolymerization initiator coloring agent menstruum C-1 C-2 C-3 C-4 Comparative Example 1 10 5 - - 0.6 - 29 56 Comparative Example 2 10 5 - - - 0.6 29 56 Comparative Example 3 10 5 - - 0.3 0.3 29 56 Example 1 10 5 0.6 - - 29 56 Example 2 10 5 One - - - 29 56 Example 3 10 5 - 0.6 - - 29 56 Example 4 10 5 - One - - 29 56 Binder resin: SPC-29L (Showa Denko)
Photopolymerizable compound: dipentaerythritol hexaacrylate
Photopolymerization initiator
C-1: A photopolymerization initiator of Synthesis Example 1
C-2: A photopolymerization initiator of Synthesis Example 2
C-3: I-369 (Basf)
C-4: OXE-01 (Basf)
Colorant: SC-P125-7146BLUE (Toyo Ink)
Solvent: propylene glycol monomethyl ether acetate

(1) Manufacture of color filters

The blue photosensitive resin composition thus prepared was applied to the top of a glass substrate by a spin coating method, then placed on a heating plate and held at a temperature of 100 캜 for 3 minutes to form a color layer thin film. Then, a test photomask having a line / space pattern of 1 to 50 mu m was placed on the test photomask, and the distance between the test photomask and the test photomask was set to 100 mu m. At this time, the ultraviolet light source was irradiated at a light intensity of 50 mJ / cm 2 using a 1 kW high pressure mercury lamp containing g, h and i lines, and no special optical filter was used. The color layer thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes for development. The glass substrate on which the developed color layer thin film was formed was washed with distilled water, dried in a nitrogen gas atmosphere, and heated for 1 hour in a heating oven at 200 ° C to thermally cure the color filter.

(1) PCT evaluation

Using the blue photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3, a coating film having a pattern formed by the above-described method for producing a color filter was obtained. The PCT process conditions were 3 atmospheric pressure, 100% humidity, and 130 ° C for 12 hr / 1 cycle. The cross-cut was followed by pressure-cookertest (PCT) Tape test was performed 1 to 3 times to determine whether or not the coated surface was peeled off. The results are shown in Table 2 below.

division Substrate adhesion ○: No pattern loss.
DELTA: pattern loss of 10% level
×: pattern loss of 50% or more 1 cycle 2cycle 3cycle Comparative Example 1 △ × × Comparative Example 2 × × × Comparative Example 3 △ × × Example 1 ○ ○ ○ Example 2 ○ ○ ○ Example 3 ○ ○ ○ Example 4 ○ ○ ○

As shown in Table 2, in Examples 1 to 4 using the blue photosensitive resin composition according to the present invention, it was confirmed that a highly reliable color filter without pattern loss during PCT test can be realized because of its excellent adhesion .

In the case of Comparative Examples 1 to 3 in which a conventional oxime ester derivative compound was used as a photoinitiator in place of the oxime ester fluorene derivative compound of the present invention, it was confirmed that the adhesiveness to the substrate after the PCT test was all lowered.

 (2) Development speed, sensitivity, pattern subtraction and pattern straightness evaluation

The development speed, sensitivity and pattern straightness of the color filter made of the blue photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated, and the results are shown in Table 3 below.

The development speed was measured by measuring the time taken for the unexposed area to completely dissolve in the developing solution at the time of development, and the minimum exposure amount required to form a thin film without pattern peeling after the development of sensitivity was measured.

In addition, when the generated pattern was evaluated by an optical microscope, the degree of peeling was indicated on the pattern. O = no peeling off of pattern,? = 1 to 3 pattern peeling, X = pattern peeling 4 And XX = torn bundle.

The pattern straightness evaluation showed the degree of irregularity and curvature on the pattern when the generated pattern was evaluated through an optical microscope. O = no error in pattern, Δ = 1 to 3 pattern errors, X = pattern 4 errors or more, XX = unexplained, or impossible to measure.

Development speed
(sec) Sensitivity
(mJ / cm ² ) Pattern peeling Pattern straightness Comparative Example 1 28 52 X X Comparative Example 2 21 48 △ X Comparative Example 3 19 50 △ △ Example 1 18 14 O O Example 2 22 17 O O Example 3 25 15 O O Example 4 27 20 O O

Referring to Table 3, it can be seen that Examples 1 to 4 prepared according to the present invention have a high developing speed, excellent sensitivity, no pattern peeling, and no pattern error. Therefore, in Examples 1 to 4, a color filter pattern having excellent quality can be produced.

On the other hand, in Comparative Examples 1 to 3 in which the oxime ester fluorene derivative compound was not used as a photopolymerization initiator, pattern peeling and pattern errors were observed on the substrate, and the sensitivity was not excellent.

Claims (8)

A photopolymerization initiator and a colorant,
Wherein the photopolymerization initiator comprises at least one oxime ester fluorene derivative represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

(In the formula 1,
Each of R ₁ to R ₃ is independently selected from the group consisting of hydrogen, a halogen group, a C1 to C20 alkyl group, a C6 to C20 aryl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, A C1 to C20 hydroxyalkyl group, a C1 to C20 hydroxyalkoxy group, a C1 to C20 alkyl group or a C3 to C20 cycloalkyl group;
R ₄ to R ₁₀ are independently selected from the group consisting of hydrogen, a C 1 to C 20 alkyl group, a C 6 to C 20 aryl group, a C 1 to C 20 alkoxy group, a C 6 to C 20 aryl group, a C to C 20 alkyl group, a C to C 20 hydroxyalkyl group, A hydroxyalkoxy group of-C20, a C1-C20 alkyl group or a C3-C20 cycloalkyl group, amino, nitro, cyano or hydroxy;
n is 0 or 1.) The method according to claim 1,
The blue photosensitive resin composition
An alkali-soluble binder resin, a photopolymerizable compound, and a solvent. 3. The method according to claim 1 or 2,
1 to 40 wt% of the alkali-soluble binder resin, 1 to 20 wt% of a photopolymerizable compound, 0.1 to 10 wt% of a photopolymerization initiator, 5 to 40 wt% of a colorant, and 20 to 85 wt% of a solvent, based on 100 wt parts of the blue photosensitive resin composition %, Based on the total weight of the composition. The method according to claim 1,
Wherein the coloring agent comprises at least one blue pigment. 5. The method of claim 4,
Wherein the colorant is at least one selected from the group consisting of CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60 And a blue light-sensitive resin composition. 6. The method of claim 5,
The colorant comprises a violet pigment of CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38 And at least one compound selected from the group consisting of the compounds represented by the general formulas (1) and (2). A color filter produced by the blue photosensitive resin composition according to any one of claims 1 to 6. A liquid crystal display device comprising the color filter according to claim 7.