KR20180089738A - Colored photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

The present invention relates to: a photopolymerization initiator comprising an oxime ester fluorene compound, a colorant comprising a rhodamine-based dye in a particulate state; and a dispersing agent comprising a triazine-based compound; and a color filter and an image display device produced using the same. An object of the present invention is to provide the colored photosensitive resin composition, which is excellent in dispersion stability, and has improved heat resistance and solvent resistance.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, and a color filter and an image display device using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the same, and an image display device.

BACKGROUND ART [0002] Color filters are widely used in various display devices such as an image pickup device and a liquid crystal display (LCD), and their application range is rapidly expanding. The color filter may be formed of three color patterns of red, green, and blue, or may be formed of three color patterns of yellow, magenta, and cyan, Lt; / RTI >

The color filter widely used in the display device is a method in which a colored photosensitive resin composition containing a pigment dispersion composition corresponding to the color of each pattern is uniformly applied on a substrate having a black matrix pattern formed thereon by spin or slit coating, The coating film formed by heat drying is exposed and developed and, if necessary, an additional heating and curing operation is repeated for each color to form pixels of each color. In addition, in the case of a developing process such as an inkjet process and a printing process A color filter is produced using a colored photosensitive resin composition using the above pigment dispersion composition as a coloring material.

Color filters using the above-mentioned colored photosensitive resin composition are required to have properties such as high luminance and high contrast. In recent years, pixels having high color reproducibility are required. Accordingly, the content of the pigment and carbon black of the coloring material used in the colored resin composition is increased. However, when the content of the coloring material in the colored resin composition is increased, the pigment must be atomized in order to exhibit excellent optical characteristics. In particular, the viscosity of the pigment dispersion composition may be increased, This results in a problem that optical characteristics such as luminance and contrast also deteriorate.

Japanese Unexamined Patent Application Publication No. 2013-61619 discloses a blue colorant composition for a color filter and a color filter substrate using the composition. The blue colorant composition for a color filter contains at least a colorant, a binder resin, a polymer dispersant and a solvent. The present invention relates to a blue colorant composition for a color filter, which comprises a pigment and a rhodamine-based dye and the rhodamine-based dye is present in a particulate state in the blue colorant composition. However, And a problem that the solvent resistance is insufficient.

Therefore, there is a need to study a colored photosensitive resin composition excellent in various dispersion stability and excellent in heat resistance and solvent resistance.

Japanese Laid-Open Patent Publication No. 2013-61619 (Apr.

It is an object of the present invention to provide a colored photosensitive resin composition excellent in dispersion stability, improved in heat resistance and solvent resistance, and improved in nicking.

Another object of the present invention is to provide a color filter and an image display device manufactured using the above-mentioned colored photosensitive resin composition.

In order to accomplish the above object, the colored photosensitive resin composition according to the present invention comprises a photopolymerization initiator comprising oxime ester fluorene compound represented by the following formula (1): A colorant comprising a rhodamine-based dye in a particulate state; And a dispersant containing a triazine-based compound:

[Chemical Formula 1]

(In the formula 1,

R ₁ to R ₅ and R ₇ to R ₁₀ are independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, A hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms,

R ₆ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 20 carbon atoms, an amino group, a nitro group, a cyano group, and a hydroxy group,

and p is an integer of 0 to 1).

The color filter and the image display apparatus according to the present invention are characterized by including the above-mentioned colored photosensitive resin composition.

 The colored photosensitive resin composition of the present invention has an advantage of excellent dispersion stability.

Further, the color filter and the image display device of the present invention have an advantage of excellent heat resistance and solvent resistance and prevent the occurrence of a line-breaking by including the above-mentioned colored photosensitive resin composition.

When a member is referred to as being " on "another member in the present invention, this includes not only when a member is in contact with another member but also when another member exists between the two members.

Whenever a part is referred to as "including " an element in the present invention, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

Hereinafter, the present invention will be described in more detail.

≪ Colored photosensitive resin composition &

A colored photosensitive resin composition according to an embodiment of the present invention comprises a photopolymerization initiator comprising an oxime ester fluorene compound represented by the following formula (1); A colorant comprising a rhodamine-based dye in a particulate state; And a dispersant containing a triazine-based compound, it is excellent in heat resistance and solvent resistance and can be prevented from nicking.

[Chemical Formula 1]

(In the formula 1,

R ₁ to R ₅ and R ₇ to R ₁₀ are independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, A hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms,

R ₆ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 20 carbon atoms, an amino group, a nitro group, a cyano group, and a hydroxy group,

and p is an integer of 0 to 1).

In the formula 1, R ₁ to R ₅ and R ₆ to R ₁₀ are specifically hydrogen, bromo, chloro, iodo, methyl, ethyl, n-propyl, i- An aryl group such as a phenyl group, a naphthyl group, a naphthyl group, a biphenyl group, a terphenyl group, an anthryl group, an indenyl group, a phenanthryl group, Propyloxy group, n-butoxy group, i-butoxy group, t-butoxy group, hydroxymethyl group, hydroxyethyl group, hydroxy n-propyl group, hydroxy 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, An ethyl group, a hydroxymethoxypropyl group, a hydroxymethoxybutyl group, a hydroxyethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, a hydroxyethoxy Group, a hydroxy-ethoxy-hexyl, and the like.

In the formula 1, R ₆ is specifically a hydrogen atom, a bromo group, a chloro group, an iodo group, a methyl group, an ethyl group, an n-propyl group, n-pentyl, i-pentyl, i-hexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, N-propyl group, hydroxy n-butyl group, hydroxy i-propyl group, n-butoxy group, i-butoxy group, t-butoxy group, hydroxymethyl group, hydroxyethyl group, -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 hydroxymethoxybutyl group, a hydroxyethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, a hydroxyethoxypentyl group, a hydroxyethoxy A hexyl group, an amino group, a nitro group, a cyano group, and a hydroxyl group.

As used herein, the term "alkyl group" means a straight or branched chain hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, free of unsaturation and bonded to the remainder of the molecule by a single bond. Specifically, the alkyl group may be a straight or branched alkyl group having 1 to 20 carbon atoms, more specifically a straight or branched alkyl group having 1 to 10 carbon atoms, more specifically, a straight or branched alkyl group having 1 to 6 carbon atoms Chain or branched alkyl group. 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, a phosphoric acid group, a hetero group of C ₁ to C ₂₀ alkyl group, C ₁ to halogenated alkyl group of C _20, C ₁ to C ₂₀ alkenyl groups, C ₁ to C ₂₀ alkynyl group, C ₁ to C ₂₀ of the, C ₆ to an aryl group of C _20, which may be substituted with a heteroaryl group of C ₆ to C ₂₀ arylalkyl group, C ₆ to C ₂₀ heteroaryl group, or C ₆ to C ₂₀ of the.

As used herein, "aryl group" means an aromatic monocyclic or multicyclic hydrocarbon ring system consisting only 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 may be an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and may comprise a single or fused ring system comprising from 4 to 7, in particular 5 or 6, ring atoms in each ring, Or a form in which the aryl is linked by a single bond. The aryl group may include 6 to 20 carbon atoms, and may specifically include 6 to 18 carbon atoms.

As used herein, the "alkoxy group" may be an oxygen-containing straight-chain or branched alkoxy group each having an alkyl moiety of 1 to 20 carbon atoms. Specifically, it may be an alkoxy group having 1 to 10 carbon atoms, more specifically, an alkoxy group having 1 to 4 carbon atoms. The alkoxy group includes, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a t-butoxy group. The alkoxy group may be further substituted with one or more halogen 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.

As used herein, the term "arylalkyl group" means that at least one hydrogen atom of the alkyl group is substituted with the aryl group. The arylalkyl group may have 7 to 40 carbon atoms, specifically 7 to 28 carbon atoms, and more specifically, 7 to 24 carbon atoms.

As used herein, the term "hydroxyalkyl group" means an OH-alkyl group in which a hydroxy group is bonded to the alkyl group defined above, and the hydroxyalkoxyalkyl group is hydroxyalkyl-O-alkyl in which the hydroxyalkyl group and the alkyl group are connected by oxygen it means. The hydroxyalkyl group may have 1 to 20 carbon atoms, specifically 1 to 10 carbon atoms, more specifically 1 to 6 carbon atoms. The hydroxyalkoxyalkyl group may have from 2 to 40 carbon atoms, specifically from 2 to 20 carbon atoms, and more specifically from 2 to 9 carbon atoms.

As used herein, the term "cycloalkyl group" may include 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 may have 3 to 20 carbon atoms, specifically 3 to 10 carbon atoms, more specifically 3 to 8 carbon atoms.

Light curing Initiator

The photopolymerization initiator is a compound for initiating a photopolymerizable compound to be described later. The colored photosensitive resin composition according to one embodiment of the present invention contains the oxime ester fluorene compound of the above formula (1) To thereby shorten the exposure time, thereby preventing tearing and improving the resolution.

The colored photosensitive resin composition of the present invention may further contain a conventional photopolymerization initiator capable of polymerizing a photopolymerizable compound to be described later in addition to the photopolymerization initiator described above within the range not hindering the object of the present invention, And may further include conventional photopolymerization initiators used in the art.

 The photopolymerization initiator which may further be contained in addition to the photopolymerization initiator including the oxime ester fluorene compound is not particularly limited as long as it is used in the art as a photopolymerization initiator. Specifically, a triazine-based compound, an acetophenone- , An oxime compound, a benzoin compound, a benzophenone compound, a thioxanthone compound, an anthracene compound, and an anthracene compound.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane -1-one oligomers and the like.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4' Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group at 4,4' An imidazole compound substituted by a haloalkoxy group, and the like. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 5,5'-tetraphenylbiimidazole is preferably used.

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

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ' Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-di (N, N'-dimethylamino) -benzophenone.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- Santon et al.

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

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl, titanocene compounds and the like can be used, but the present invention is not limited thereto.

When the photopolymerization initiator is used in combination with the photopolymerization initiator described above, the colored photosensitive resin composition containing the photopolymerization initiator can have a higher sensitivity, and the productivity can be improved by using the photopolymerization initiator.

The photopolymerization initiator can be used without any particular limitations as long as it is used in the art, and specific examples thereof include an amine compound and a carboxylic acid compound.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amines such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, N, N-dimethyl para-toluidine, 4,4'-bis (dimethylamino) benzophenone Amino) benzophenone, and more specifically an aromatic amine compound can be preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, And aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The content of the photopolymerization initiator may be in the range of 0.1 to 20% by weight, more preferably 1 to 10% by weight based on 100% by weight of the total solid content of the colored photosensitive resin composition containing the photopolymerization initiator. When the content of the photopolymerization initiator is within the above range, the sensitivity efficiency of the colored photosensitive resin composition containing the photopolymerization initiator improves, and the productivity of the color filter manufactured using the photopolymerizable composition can be improved.

According to one embodiment of the present invention, the photopolymerization initiator may be contained in an amount of 0.1 to 20% by weight, specifically 1 to 12% by weight, based on 100% by weight of the total solid content of the colored photosensitive resin composition containing the same. When the photopolymerization initiator is contained within the above range, the sensitivity of the colored photosensitive resin composition containing the photopolymerization initiator is improved, the exposure time is shortened, the productivity is improved, high resolution can be maintained, and the strength of the pixel portion and the smoothness There is an advantage to be lost. If the content of the photopolymerization initiator is less than the above range, the degree of curing may be insufficient, which may cause problems in pattern formation. If the content is in excess of the above range, the generation of gas during the pattern formation process may increase, have.

coloring agent

Rhodamine-based dye

The colored photosensitive resin composition according to an embodiment of the present invention has an advantage that a color filter containing a rhodamine-based dye present in a particle state is included, thereby making it possible to produce a high-luminance color filter.

According to one embodiment of the present invention, the rhodamine-based dye is C.I. Acid Red 52, 87, 91, 92, 94, 289; C.I. Acid Yellow 73; C.I. Basic Red 1; C.I. Basic violet 10, 11; And C.I. Solvent Red 49. < / RTI >

Although it is not desired to be limited by the theory, since the dye is dissolved in the composition in a color filter substrate using a general dye, the contrast ratio is lowered by dry coagulation during prebaking, oxidation of dye molecules due to ultraviolet A decrease in the contrast ratio due to sublimation or the like of the dye molecules in the post-baking may occur.

However, since the rhodamine-based dye is present in the form of particles in the present invention, the rhodamine-based dye is stably maintained in the particle state even after application, drying, exposure, development, and post-baking, And the contrast ratio is excellent.

The rhodamine-based dye may be insoluble in propylene glycol monomethyl ether acetate (PGMEA), which is an ester-based solvent. The PGMEA is a solvent that is widely used in colored photosensitive resin compositions using pigments because of its excellent stability, coating properties, drying properties, and dispersion stability of pigments. When the rhodamine-based dye is insoluble in the PGMEA, And the pigments and the rhodamine-based dyes to be described later can be stably present in the PGMEA as a particle state.

It is preferable that the rhodamine-based dye is purified to remove ionic impurities contained in the rhodamine-based dye. For example, the sum of the ionic impurities such as Na ⁺ , Cl ^- , and SO ₄ ^2- contained in the rhodamine-based dye is preferably 20,000 ppm or less, more preferably 10,000 ppm or less. When the sum of the ionic impurities such as Na ⁺ , Cl ^- , and SO ₄ ^2- contained in the rhodamine-based dye is 20,000 ppm or less, it is possible to prevent the dispersion stability of the PGMEA from being degraded by ionic impurities There is an advantage.

The method for purifying the rhodamine-based dye is not limited to the method commonly used in the art, but may be, for example, a reprecipitation method, a recrystallization method, a reverse osmosis method, or ion exchange with an ion exchange resin (cation exchange resin, anion exchange resin) Can be used.

Whether the rhodamine-based dye is present in the colored photosensitive resin composition in a particle state can be confirmed by using a particle size analyzer (accusizer 780A).

To determine whether the rhodamine-based dye is in a particle state or a molecular state in a color filter prepared from the colored photosensitive resin composition of the present invention, for example, a blue pixel of a color filter is determined by FIB-TEM analysis and EDX element analysis as follows can do. Since the pigment particles and the rhodamine-based dye particles are mixed in the color filter, 100 particles are analyzed. Since the particle diameter of the pigment and the rhodamine-based dye is 10 to 500 nm, the measurement diameter of the FIB-TEM is 1 to 10 nm. After observing the FIB-TEM, elemental analysis is performed on the observation portion by EDX. When the EDX analysis result of 100 particles is compared with the EDX analysis result of the rhodamine dye itself, if the number of the particles of which the analysis result agrees is 1 to 100, whether or not the rhodamine dye is present in a particle state .

Whether or not the rhodamine-based dye is included in the colored photosensitive resin composition can be determined by, for example, laser Raman spectroscopy. That is, the above-mentioned colored photosensitive resin composition is applied, the solvent is dried, exposed, developed, and post-baked to manufacture pixels. By comparing the laser Raman spectroscopic spectrum of the thus-produced pixel with the laser Raman spectroscopic spectrum of the rhodamine-based dye itself, it is possible to determine whether or not the rhodamine-based dye is contained in the colored photosensitive resin composition.

The average particle diameter of the rhodamine-based dye and pigments described later is preferably 30 to 200 nm, more preferably 30 to 100 nm. When the average particle diameter of the rhodamine-based dye and a pigment to be described later exceeds 200 nm, the transmittance and the contrast ratio may be somewhat lowered by scattering of the particles, and when the average particle diameter of the rhodamine-based dye is less than 30 nm, The alkali solubility of the resin is somewhat lowered and the pattern processability may be somewhat lowered.

The average particle diameter of the rhodamine dyes and pigments described later can be controlled within the above range by applying shear stress to the rhodamine-based dyes and pigments described later using zirconia beads using a dispersing machine such as a sand mill or a ball mill.

However, it is somewhat difficult to control the average particle diameter of the rhodamine-based dye within the above-mentioned range under conventionally known dispersion conditions of the pigment. That is, in the pigment powder, primary particles assembled at about 30 nm are collected to form powder particles of several 탆. Since the cohesive force of the primary particles is small, the pigment powder can disperse the primary particles with a relatively short shear stress in a short period of time, thereby making the average particle diameter 30 to 200 nm. However, the dye powder aggregates molecules of about 1 nm and is formed of coarse particles of several 탆. Since the cohesive force of the molecules of the dye powder is strong, it is somewhat difficult to make the average particle diameter smaller than 200 nm with a weak shear stress. Further, since primary particles are not present in the dye, if the shear stress is strengthened or the dispersing time is increased, the average particle diameter may be smaller than 30 nm.

Therefore, it is preferable to disperse the rhodamine-based dyes and pigments described later in different dispersion conditions in order to make the average particle diameter of the rhodamine-based dyes and pigments described later to 30 to 200 nm.

As the dispersing conditions of the rhodamine-based dye, zirconia beads having a bead diameter of 0.3 to 2.0 탆 are preferably used, and the dispersing time is preferably 3 to 10 hours / kg under a strong shear stress. As the dispersing conditions of the pigment, It is preferable to use zirconia beads having a thickness of 2.0 占 퐉 for a dispersion time of 1 to 10 hours / kg.

In the present invention, it is preferable that the rhodamine-based dye dispersion and the pigment dispersion separately subjected to the dispersion process are mixed and then further dispersed. By this process, the average particle size of the rhodamine-based dye and the pigment can be controlled within the range of 30 to 100 nm, and the contrast ratio can be further improved by improving the transmittance and the luminance.

As the further dispersion condition of the mixed dispersion, it is preferable to use a zirconia bead having a bead diameter of 0.01 to 0.2 탆 and a dispersion time of 0.1 to 3 hours / kg with a weak shear stress.

Further, since the colored photosensitive resin composition according to an embodiment of the present invention includes a dispersant containing a rhodamine-based dye dispersed and stabilized in the composition together with a triazine-based compound, the luminance is further improved as compared with the case where the rhodamine- There is an advantage that deterioration of the contrast ratio can be prevented.

The rhodamine-based dye may be contained in an amount of 1 to 80 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the entire colorant dispersion. When the rhodamine-based dye is included within the above range, it is preferable in terms of dispersion stability and transmittance. When the rhodamine-based dye is included in the range below the above range, the transmittance may be somewhat lowered, and if it exceeds the above range, the dispersion stability may be somewhat lowered due to aggregation of the dye.

Pigment

The colored photosensitive resin composition according to one embodiment of the present invention may further comprise a pigment together with the rhodamine-based dye described above.

The pigment may be an organic pigment or an inorganic pigment generally used in the art. The above-mentioned pigments can be used in various kinds of pigments used in printing ink, ink jet ink and the like. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, And an anthanthrone pigment, an anthanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like, but are not limited thereto.

Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or a composite metal oxide, but are not limited thereto.

Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number Pigments, but are not limited thereto.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 , 185;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, 264;

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, 38;

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64, 76;

C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58, 59, 62, 63;

C.I. Pigment Brown 28;

C.I. Pigment Black 1, 7; Etc

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

The exemplified C.I. Among the pigment pigments, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6 can be preferably used.

It is preferable to use a colorant dispersion in which the particle diameter of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment by adding a pigment dispersant. According to this method, a colorant dispersion in which the pigment is uniformly dispersed in a solution can be obtained Do.

The pigment dispersant may be added separately from a dispersant containing a triazine-based compound to be described later, and examples thereof include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine , Which may be used alone or in combination of two or more, but the present invention is not limited thereto.

The content of the pigment is in the range of 1 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the whole colorant dispersion. When the content of the pigment is in the range of 1 to 50 parts by weight, the viscosity is low, the storage stability is excellent, and the dispersing efficiency is high, which is effective for increasing the contrast ratio.

In addition, the colorant dispersion may further include a dispersion medium.

The dispersion medium is added for maintenance of deaggregation and stability of the pigment, and any of those generally used in the art can be used without limitation. (Hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant prepared by a living control method as disclosed in Korean Patent Laid-Open Publication No. 2004-0014311. DISCLOSURE OF INVENTION It is an object of the present invention to provide an acrylic dispersant, 2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

The acrylic dispersants exemplified above may be used alone or in combination of two or more.

As the dispersion medium, other resin type pigment dispersants other than the acrylic dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oily dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters. DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-160, BYK (trade name) 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co., In addition to the above acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylic dispersant.

The pigment dispersant may be contained in an amount of 0.1 to 30 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. When the content of the pigment dispersant satisfies the above range, the contrast and stability can be improved.

Dispersant containing a triazine compound

The colored photosensitive resin composition according to one embodiment of the present invention includes a dispersant containing a triazine-based compound. The triazine-based compound is not limited thereto as long as it is a substance known in the art as a dispersant. For example, the triazine type dispersant described in JP-A-2008-214515 and JP-A-2011-032374 can be used.

According to one embodiment of the present invention, the triazine-based compound may be represented by the following general formula (2).

(2)

(In the formula (2)

R ₁₁ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, and an -NR ₁₂ R ₁₃ group,

R ₁₂ and R ₁₃ are each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms,

Wherein the alkyl group and the alkoxy group are substituted or unsubstituted with a hydroxyl group or a straight or branched alkoxy group having 1 to 20 carbon atoms.

In Formula 2, the alkyl group having 1 to 20 carbon atoms is specifically a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a sec-propyl group, a n-butyl group, an isobutyl group, The alkoxy group having 1 to 20 carbon atoms is specifically exemplified by methoxy, ethoxy, n-propoxy, isopropoxy, sec-propoxy, n-butoxy, isobutoxy, sec -Butoxy group, and tert-butoxy group.

When the triazine-based compound is included, the pigment and the rhodamine-based dye can be uniformly dispersed in various media. Accordingly, the colored photosensitive resin composition according to an embodiment of the present invention includes the dispersant containing the triazine-based compound, thereby suppressing the re-aggregation of the colorant containing the rhodamine-based dye and increasing the viscosity thereof, have.

Among the dispersants, when the triazine-based compound is used in combination with a resinous dispersant, the effect of improving the dispersibility of the rhodamine-based dye and the pigment and the effect of suppressing re-aggregation may become remarkable.

In addition, since the triazine-based compound exhibits white color in the visible region, an image display device capable of coloring with high brightness can be manufactured by the color filter formed from the colored photosensitive resin composition containing the triazine-based compound. The colored photosensitive resin composition prepared using the triazine-based compound has a relatively low initial viscosity and a high effect of suppressing the re-aggregation of the pigment, so that the storage stability of the dispersing agent is excellent and the increase in viscosity due to storage is relatively small .

The triazine-based compound may be contained in an amount of 0.1 to 60 parts by weight based on 100 parts by weight of the entire colorant. When the triazine-based compound is contained within the above range, crystal growth of the rhodamine-based dye and the pigment can be inhibited. When the triazine-based compound is contained in an amount less than the above range, the rhodamine-based dye may agglomerate, and if it exceeds the above range, the contrast ratio may be somewhat lowered.

The colored photosensitive resin composition according to one embodiment of the present invention may further include at least one selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a solvent and an additive.

Alkali-soluble resin

The colored photosensitive resin composition according to one embodiment of the present invention may further comprise an alkali-soluble resin.

The alkali-soluble resin is polymerized to include an ethylenically unsaturated monomer having a carboxyl group. This is a component that imparts solubility to an alkali developing solution used in a developing process when a pattern is formed.

The ethylenically unsaturated monomer having a carboxyl group is not particularly limited, and examples thereof 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 thereof; mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate, and the like, preferably acrylic acid and methacrylic acid. These may be used alone or in combination of two or more.

The alkali-soluble resin may be polymerized by further comprising at least one other monomer copolymerizable with the monomer. Methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p- Aromatic vinyl compounds such as 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; Acrylate such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate and isobornyl Alicyclic (meth) acrylates; 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, and the like. These may be used alone or in combination of two or more.

In the present specification, (meth) acrylate means acrylate or methacrylate.

The content of the alkali-soluble resin is not particularly limited, and is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, based on 100% by weight of the total solid content of the colored photosensitive resin composition More preferable. When the content of the alkali-soluble resin is within the above range, solubility in a developing solution is sufficient and pattern formation is easy, and reduction in film thickness of the pixel portion of the exposed portion is prevented at the time of development, so that the missing property of the non- .

Photopolymerization  compound

The colored photosensitive resin composition according to one embodiment of the present invention may further comprise a photopolymerizable compound.

The photopolymerizable compound is not particularly limited as long as it is a compound capable of polymerizing under the action of a photopolymerization initiator described later. Preferably, a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound or a trifunctional or higher functional polyfunctional photopolymerizable compound .

Specific examples of the monofunctional photopolymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- And vinyl pyrrolidone. Commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), and Viscot 158 (Osaka Yuki Kagaku Kogyo).

Specific examples of the bifunctional photopolymerizable compound include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (Acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate and the like. Commercially available products include Aronix M-210, M-1100 and 1200 (Doagosei) KAYARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Yuki Kagaku Kogyo), AH-600, AT-600 or UA-306H (Kyoeisha Chemical Co., Ltd.) and the like.

Specific examples of the polyfunctional photopolymerizable compound having three or more functional groups include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku), and the like.

Of the photopolymerizable compounds exemplified above, trifunctional or higher (meth) acrylate esters and urethane (meth) acrylates are particularly preferable because they have excellent polymerizability and can improve the strength.

The photopolymerizable compounds exemplified above may be used alone or in combination of two or more.

The photopolymerizable compound may be contained in an amount of 5 to 70% by weight, preferably 10 to 60% by weight, more preferably 15 to 50% by weight based on 100% by weight of the total solid content of the yellow curable resin composition. When the photopolymerizable compound is contained within the above range, there is an advantage that the strength and smoothness of the pixel portion are good.

solvent

The colored photosensitive resin composition according to one embodiment of the present invention may further comprise a solvent.

The solvent may be any solvent used in the art without any particular limitation, and various organic solvents may 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, Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate; Alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as? -butyrolactone.

The solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in the solvent in terms of coating property and drying property, more preferably an alkylene glycol alkyl ether acetate, a ketone, a 3-ethoxypropionic acid Ethyl, and 3-methoxypropionate, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl propoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent is preferably 60 to 90% by weight, more preferably 70 to 85% by weight based on 100% by weight of the total of the colored photosensitive resin composition. When the content of the solvent is within the above range, the coating property can be improved when applied by a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) .

additive

The colored photosensitive resin composition according to one embodiment of the present invention may further include an additive.

The additive may be optionally added, for example, other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti-aggregation agent.

Specific examples of the other polymer compound include a curable resin such as an epoxy resin and a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane But is not limited thereto.

The curing agent is used for increasing the curing depth and mechanical strength, and specifically includes, but is not limited to, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

More specifically, the epoxy compound in the curing agent may be at least one selected from the group consisting of a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a novolak epoxy resin and other aromatic epoxy resins, Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than glycidyl ester resins, glycidyl amine resins, brominated derivatives of the above epoxy resins, epoxy resins and their brominated derivatives ) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

More specifically, examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used in combination with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound.

The curing auxiliary compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of the commercially available products include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Rikashido HH (manufactured by Shin-Nihon Ehwa Co., Ltd.), and MH-700 (manufactured by Shin-Etsu Chemical Co., Ltd.). The above-mentioned curing agent and curing auxiliary compound may be used alone or in combination of two or more.

The surfactant may be used to further improve the film formation of the colored photosensitive resin composition, and silicon, fluorine, ester, cationic, anionic, nonionic, amphoteric surfactant and the like may be preferably used.

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH-8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4445 and TSF-4446 from GE Toshiba Silicone Co., , TSF-4460 and TSF-4452.

Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated.

Other commercially available products include KP (Shinetsugaku Kagaku Kogyo Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC Asoui guard, Surflon (available from Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) (available from Dainippon Ink and Chemicals Inc.), Flourad (Sumitomo 3M Co., Ltd.) , EFKA (EFKA Chemical), PB 821 (Ajinomoto), and Disperbyk-series (BYK-chemi).

Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, quaternary ammonium salts, and the like.

Examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

The nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

The above-mentioned surfactants may be used alone or in combination of two or more.

The type of the adhesion promoter is not particularly limited and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, -Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

These adhesion promoters may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total weight of the solid content of the red photosensitive resin composition.

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

The ultraviolet absorber is not particularly limited, but specific examples thereof include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone .

The kind of the anti-aggregation agent is not particularly limited, but specific examples that can be used include sodium polyacrylate and the like.

<Color filter>

Another aspect of the present invention relates to a color filter which is produced using the above-mentioned colored photosensitive resin composition and which is excellent in developability and heat resistance, has improved brightness, and does not generate residue during development.

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

The substrate may be the substrate of the color filter itself, or may be a portion where a 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 (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer may be a layer including the colored photosensitive resin composition of the present invention, and may be a layer formed by applying the colored photosensitive resin composition and exposing, developing, and thermosetting the colored photosensitive resin composition in a predetermined pattern. The pattern layer may be formed by performing a method commonly known in the art.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between each pattern, and may further include a black matrix, but is not limited thereto.

Further, the color filter may further include a protective film formed on the pattern layer of the color filter.

<Image Display Device>

Still another aspect of the present invention relates to an image display device including the above-described color filter, which has excellent developability and heat resistance, has improved brightness, and does not generate a residue during development.

The image display apparatus of the present invention is provided with the above-described color filter, and a specific example thereof is a liquid crystal display, an OLED, a flexible display, and the like, but is not limited thereto.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "part" representing the contents are by weight unless otherwise specified.

Synthetic example

Synthetic example  1: Triazine compound 1

18.4 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine and 21 parts by weight of 3- (2-ethylhexyloxy) propylamine were added to 100 parts by weight of water, Lt; / RTI &gt; The obtained reaction product was reacted at 85 캜 for 5 hours. The resulting reaction product was leached, washed with water, and then allowed to stand in a thermostatic chamber at 100 캜 overnight and dried to obtain a compound represented by the following formula (3).

(3)

Synthetic example  2: triazine compound 2

18.4 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine and 21 parts by weight of butylamine were added to 100 parts by weight of water and reacted at 10 DEG C for 1 hour. The obtained reaction product was reacted at 85 캜 for 5 hours. The obtained reaction product was leached, washed with water, and then allowed to stand in a thermostatic chamber at 100 캜 overnight and dried to obtain a compound represented by the following formula (4).

[Chemical Formula 4]

Synthetic example  3: Fluorene-based  compound

Reactants 1.

200 mg of fluorene, 268.8 g of potassium hydroxide and 19.9 g of potassium iodide were dissolved in 1 L of anhydrous dimethyl sulfoxide under nitrogen atmosphere, 283.3 g of bromoethane was slowly added over 2 hours while the reaction was maintained at 15 占 폚, The reaction was stirred at 15 &lt; 0 &gt; C for 1 hour. Then, 2 L of distilled water was added to the reaction mixture, and the mixture was stirred for 30 minutes. The product was extracted with 2 L of dichloromethane. The extracted organic layer was washed twice with 2 L of distilled water. The organic layer was dried over anhydrous magnesium sulfate, The resulting product was subjected to fractional distillation under reduced pressure to obtain 248.6 g of a pale yellow reaction product 1 (9,9-diethyl-9H-fluorene) having a high viscosity.

Reactants 2.

100.5 g of the above Reaction product 1 was dissolved in 1 L of dichloromethane, and the reaction product was cooled to -5 캜. Then, 72.3 g of aluminum chloride was slowly added thereto. While taking care not to raise the temperature of the reaction product, g &lt; / RTI &gt; was added slowly over 2 hours and stirred at -5 &lt; 0 &gt; C for 1 hour. Then, the reaction mixture was slowly poured 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 (eluent ethyl acetate: (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione-2-oxime), which was a pale yellow solid, 27.5 g.

Reactants 3.

After dissolving 44.5 g of the above Reaction Product 2 in 900 ml of tetrahydrofuran (THF), 150 ml of 4N HCl dissolved in 1,4-dioxane and 24.7 g of isobutyl nitrite were added in turn, and the reaction was stirred at 25 ° C for 6 hours Lt; / RTI &gt; 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: = 1: 6 mixed solvent and then dried again to obtain a reaction product 3 (1- (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione -2-oxime).

Reactants 4.

The reactant 3 was dissolved in 1 L of N-methyl-2-pyrrolidinone (NMP) under a nitrogen atmosphere, and the reaction was maintained at -5 ° C. Then, 35.4 g of triethylamine was added and the mixture was stirred for 30 minutes. Pyrrolidinone in 75 ml of N-methyl-2-pyrrolidinone was added slowly over 30 minutes, and the mixture was stirred for 30 minutes while careful not to raise the temperature of the reaction. 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 again to obtain C-2 (1- (9,9-diethyl-9H-fluoren-2-yl) Oxime-0-acetate).

Synthetic example  4: Alkali-soluble resin

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was provided with 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were charged and stirred to prepare a charge transfer additive dropping funnel. To this was added n-dodecanethiol And 24 g of PGMEA were placed and stirred and mixed. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C with stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The mixture was allowed to proceed for 2 hours each while maintaining the temperature at 90 캜. After 1 hour, the temperature was elevated to 110 캜 and maintained for 3 hours. Then, a gas introduction tube was introduced to obtain an oxygen / nitrogen mixed gas of 5/95 (v / v) And started bubbling. Then, 28.4 g of [(0.10 mol) of glycidyl methacrylate, 33 mol% of the carboxyl group of the acrylic acid used in the present reaction), 2,2'-methylenebis (4-methyl-6-t- ) And 0.8 g of triethylamine were placed in a flask, and the reaction was continued at 110 캜 for 8 hours to obtain an alkali-soluble resin having a solid acid value of 70 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 16,000 and the molecular weight distribution (Mw / Mn) was 2.3.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial connection)

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection amount: 50 μl

Detector: RI

Measurement sample concentration: 0.6 mass% (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)

 The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

Manufacturing example

Manufacturing example  1: Colorant dispersion 1 (A-1)

20.48 parts by weight of the compound of the formula (3) synthesized in Synthesis Example 1 as a triazine derivative, Pigment Blue 15: 6 9.12 parts by weight, C.I. 2.88 parts by weight of Acid Red 52, 3.84 parts by weight of an acrylic dispersant (DisperBYK-2000, manufactured by Big Chemical), 2.88 parts by weight of a resin of Synthesis Example 4, 55.04 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.76 parts by weight of propylene glycol monomethyl ether And 360 parts by weight of zirconia beads having a diameter of 0.2 mm were put into a mayonnaise bottle having a volume of 140 ml and kneaded at 60 캜 for 10 hours by a paint conditioner to carry out dispersing treatment. Thereafter, zirconia beads were removed to obtain a dispersion. The dispersion was filtered with a membrane filter having a pore size of 1.0 탆 to obtain a colorant dispersion 1.

Manufacturing example  2: Colorant dispersion 2 (A-2)

The procedure of Preparation Example 1 was repeated except that the compound of Formula 4 synthesized in Synthesis Example 2 was used as the triazine derivative.

Manufacturing example  3: Colorant dispersion 3 (A-3)

The procedure of Preparation Example 1 was repeated except that the triazine derivative was not used.

Manufacturing example  4: Colorant dispersion 4 (A-4)

Instead of Acid Red 52, C.I. Pigment Violet 23 was used instead of Pigment Violet 23.

Example  And Comparative Example

The colored photosensitive resin compositions of Examples and Comparative Examples were prepared according to the compositions shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Colorant dispersion A-1 12 - 12 - 14 - 12 - - A-2 - 12 - 12 - - - 12 - A-3 - - - - - 12 - - - A-4 - - - - - - - - 12 Photopolymerization initiator B-1 3 3 1.5 1.5 5 3 - - 3 B-2 - - 1.5 1.5 - - 3 3 - Photopolymerization
compound C 8 8 8 8 8 8 8 8 8 Alkali-soluble resin D 8 8 8 8 8 8 8 8 8 solvent E 68.5 68.5 68.5 68.5 68.5 68.5 68.5 68.5 68.5 additive F 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 A-1: Colorant dispersion 1 of Production Example 1
A-2: Colorant dispersion 2 of Production Example 2
A-3: Colorant dispersion 3 of Production Example 3
A-4: Colorant dispersion 4 of Production Example 4
B-1: Fluorene compound of Synthesis Example 3
B-2: Irgacure OXE02 (manufactured by BASF)
C: dipentaerythritol hexaacrylate (KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.)
D: Copolymer of methacrylic acid and benzyl methacrylate (the molar ratio of methacrylic acid unit to benzyl methacrylate unit was 31:69, acid value was 100 mgKOH / g, weight average molecular weight in terms of polystyrene was 20,000)
E: Propylene glycol monomethyl ether acetate
F: SH-8400 (manufactured by Dow Corning)

Experimental Example

Experimental Example  One: Chop  evaluation

Each of the colored photosensitive resin compositions prepared in Examples and Comparative Examples was coated on a 5 × 5 cm glass substrate, dried, and then bar-coated to a thickness of 2.5 μm. Thereafter, the solvent was removed by drying in an oven at 100 ° C. for 3 minutes. The solvent was removed to expose the dye to a total dose of 40 mJ at a wavelength of 313 nm of the fusion lamp of 300 μm with a photomask. Min, then taken out again, then immersed in distilled water for 1 minute, and then taken out and cured in an oven at 230 DEG C for 20 minutes to prepare a color filter.

The degree of the pattern peeling phenomenon of the color filter was measured, and the criteria were determined as follows. The results are shown in Table 2 below.

<Evaluation Criteria>

○: No peeling on the pattern

?: 1 to 3 on the pattern

X: 4 or more marks on the pattern

Experimental Example  2: Measurement of luminance

A color filter was prepared by using the colored photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 in the same manner as in Experimental Example 1 above. The prepared color filter was set in a spectrocolorimetric colorimeter (CM-3700d, manufactured by Konica Minolta Sensing Co., Ltd.), and the transmission chromaticity in the X, Y and Z coordinate axes at 2 ° of C light source was measured. Value was employed as luminance. The results are shown in Table 2 below.

The luminance values shown in the following Table 2 are shown as relative values when the luminance of the color filter manufactured using the colored photosensitive resin composition of Comparative Example 1 is set to the standard (100).

Experimental Example  3: Heat resistance measurement

A color filter was prepared by using the colored photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 in the same manner as in Experimental Example 1 above. The prepared color filter was subjected to comparative evaluation of the color change before and after 230 占 폚 for 2 hours. The color filter was set in a spectrocolorimetric colorimeter (CM-3700d, manufactured by Konica Minolta Sensing Co., Ltd.), and L *, a * and b * values at a C light source of 2 ° were measured. The color change in the three-dimensional colorimeter defined by L *, a *, b * is calculated by Equation (1), and the smaller the color change value, the more reliable the color filter. The results are shown in Table 2 below.

[Equation 1]

△ Eab * = [(△ L *) 2 + (△ a *) 2 + (△ b *) 2] 1/2

Experimental Example  4: Solvent resistance  evaluation

A color filter was prepared by using the colored photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 in the same manner as in Experimental Example 1 above. The prepared color filter was immersed in N-methylpyrrolidone (NMP) solution for 30 minutes, washed with ultrapure water and dried on a hot plate heated to 120 DEG C for 2 minutes, and the color change before and after immersion was measured.

At this time, the color change proceeded in the same manner as in Experimental Example 2, and the results are shown in Table 2 below. The smaller the color change value, the more reliable the color filter.

Experimental Example  5: Evaluation of occurrence of stain

A color filter was prepared by using the colored photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 in the same manner as in Experimental Example 1 above. The color filter prepared above is immersed in a KOH aqueous solution having a pH of 10.5 for 3 minutes and then taken out. The color filter is then immersed in distilled water for 1 minute and taken out, followed by curing in an oven at 230 DEG C for 20 minutes. Half of the color filter was immersed in distilled water for 10 minutes, and then nitrogen gas was blown to dry.

Whether or not staining occurred in the portion immersed in distilled water and in the portion not immersed was observed with a surface inspection lamp (FR-100R). Evaluation criteria were as follows, and the results are shown in Table 2 below.

&Lt; Evaluation criteria of stain occurrence >

○: No staining caused by distilled water

X: stain caused by distilled water

Chop Luminance Heat resistance Solvent resistance stain Example 1 ○ 1.13 1.21 1.01 ○ Example 2 ○ 1.09 1.31 1.03 ○ Example 3 ○ 1.3 1.82 1.26 ○ Example 4 ○ 1.11 2.09 1.54 ○ Example 5 ○ 1.07 1.56 1.34 ○ Comparative Example 1 △ One 4.74 5.74 × Comparative Example 2 × 1.06 3.01 3.62 × Comparative Example 3 × 1.03 3.24 3.84 × Comparative Example 4 ○ 0.63 1.23 1.34 ○

In Table 2, when a colorant containing a rhodamine-based dye in a particle state, a dispersing agent containing a triazine-based compound, and a photopolymerization initiator containing the oxime ester fluorene-based compound of the present invention were both included, (Comparative Example 1) and the oxime ester fluorene compound (Comparative Example 2 and Comparative Example 3) than the triazine type compound (Comparative Example 1) and the triazine type compound (Comparative Example 1) , No staining due to distilled water occurred during the development process, and the brightness was superior to that in the case of not including the rhodamine-based dye (Comparative Example 4).

Claims (8)

A photopolymerization initiator comprising an oxime ester fluorene compound represented by the following formula (1);
A colorant comprising a rhodamine-based dye in a particulate state; And
And a dispersing agent containing a triazine-based compound. The colored photosensitive resin composition according to claim 1,
[Chemical Formula 1]

(In the formula 1,
R ₁ to R ₅ and R ₇ to R ₁₀ are independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, A hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms,
R ₆ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 20 carbon atoms, an amino group, a nitro group, a cyano group, and a hydroxy group,
and p is an integer of 0 to 1). The method according to claim 1,
Wherein the colored photosensitive resin composition further comprises at least one selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a solvent, and an additive. The method according to claim 1,
Wherein the triazine-based compound is represented by the following general formula (2): &lt; EMI ID =
(2)

(In the formula (2)
R ₁₁ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, and an -NR ₁₂ R ₁₃ group,
R ₁₂ and R ₁₃ are each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms,
Wherein the alkyl group and the alkoxy group are substituted or unsubstituted with a hydroxyl group or a straight or branched alkoxy group having 1 to 20 carbon atoms). The method according to claim 1,
Wherein the oxime ester fluorene-based photopolymerization initiator is contained in an amount of 0.1 to 20% by weight based on 100% by weight of the total of the colored photosensitive resin composition containing the oxime ester fluorene-based photopolymerization initiator. The method according to claim 1,
The colored photosensitive resin composition of claim 1, wherein the coloring agent further comprises a pigment. The method according to claim 1,
The rhodamine dyes include CI Acid Red 52, 87, 91, 92, 94, 289; CI Acid Yellow 73; CI Basic Red 1; CI Basic Violet 10, 11; And CI Solvent Red 49. The colored photosensitive resin composition according to claim 1, A color filter comprising a cured product of the colored photosensitive resin composition according to any one of claims 1 to 6. An image display device comprising the color filter of claim 7.