KR20180089695A - Colored photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, a color filter and an image display device manufactured using the same. The colored photosensitive composition comprises: a photopolymerizable compound having at least one moiety selected from a group consisting of oxyethylene and oxypropylene in the molecular structure and having at least three functionalities of an urethane acrylic structure or a structural analog thereof; a colorant comprising a rhodamine-based dye in a particulate state; and a dispersant comprising a triazine-based compound.

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. Discloses a blue colorant composition for a color filter comprising a pigment and a rhodamine-based dye, wherein the rhodamine-based dye is present in a particle state in the blue colorant composition, but the dispersion stability is not excellent, There is a problem that the luminance of the color filter is not sufficient.

Therefore, development of a colored photosensitive resin composition capable of producing a color filter excellent in various dispersion stability and luminance has been demanded.

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

An object of the present invention is to provide a colored photosensitive resin composition excellent in dispersion stability and excellent in developability.

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 achieve the above object, the colored photosensitive resin composition according to the present invention comprises at least one moiety selected from the group consisting of oxyethylene and oxypropylene in a molecular structure, and at least one urethane acrylate or its structural a photopolymerizable compound; A colorant comprising a rhodamine-based dye in a particulate state; And a dispersant containing a triazine-based compound.

The color filter and the image display device according to the present invention are characterized by including a cured product of the above-mentioned colored photosensitive resin composition.

The colored photosensitive resin composition of the present invention is excellent in dispersion stability and developability and has an advantage of minimizing defects such as residues and unevenness in manufacturing a color filter.

Further, the color filter and the image display apparatus of the present invention have an advantage of having excellent heat resistance and brightness and excellent driving characteristics by including a cured product of 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 &

The colored photosensitive resin composition according to an embodiment of the present invention includes at least one moiety selected from the group consisting of oxyethylene and oxypropylene in the molecular structure, and is a trifunctional or more urethane acrylic system or a structural analog thereof Photopolymerizable compounds; A colorant comprising a rhodamine-based dye in a particulate state; And a dispersant containing a triazine-based compound, it has an advantage of excellent dispersion stability, and improves developability, heat resistance and brightness of a color filter and an image display device manufactured using the same, There is an advantage.

Photopolymerization  compound

The colored photosensitive resin composition according to an embodiment of the present invention includes a photopolymerizable compound containing at least one moiety selected from the group consisting of oxyethylene and oxypropylene in the molecular structure and having at least three functionalities of a urethane acrylic structure or a structural analog thereof.

According to an embodiment of the present invention, the photopolymerizable compound may be represented by the following general formula (1).

[Chemical Formula 1]

(In the formula 1,

R < ₁ > is selected from the group consisting of hydrogen and a methyl group,

R < ₂ > are each independently selected from the group consisting of hydrogen and methyl groups,

R ₃ is selected from the group consisting of -NHCOO-, -COONH-, -NHCONH-, -NHCOS- and -SCONH-,

R < ₄ > is selected from the group consisting of an aliphatic alkyl having 3 to 50 carbon atoms, an unsaturated alkyl, a cycloalkyl and an aromatic group,

m is an integer of 3 to 12, and n is an integer of 1 to 10).

The photopolymerizable compound according to one embodiment of the present invention is a photopolymerizable compound having at least one moiety selected from the group consisting of ethylene oxide and oxypropylene in the molecular structure and is a trifunctional or more urethane acrylic system or a structural analog thereof, And exhibits a rapid developing rate as compared with a photopolymerizable compound not containing an oxyethylene or oxypropylene moiety and has an advantage that a development residue is not generated.

As used herein, the term "urethane acrylic or its structural analogue" refers to an acrylic compound containing a urethane group (-NHCOO-) or a structural analog thereof, a ureido group (-NHCONH-) or a thiourethane group (-NHCOS-) .

As used herein, the term "aromatic group" may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a terphenyl group and the like. The aromatic heterocyclic group includes specifically furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, Pyridazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, There can be mentioned quinazoline, cinnoline, phthyridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole and tetrazaine.

The photopolymerizable compound can be prepared by reacting (meth) acrylic acid with hydroxy (meth) acrylate having at least one selected from the group consisting of ethylene oxide and propylene oxide and trifunctional or higher isocyanate. The photopolymerizable compound may be prepared by reacting an acrylic isocyanate with a polyfunctional alcohol to which at least one selected from the group consisting of ethylene oxide and propylene oxide is added.

Specific examples of the hydroxy (meth) acrylate include ethylene oxide ring-opened hydroxymono (meth) acrylate having a repeating unit of 1 to 50, propylene oxide ring-opening hydroxymono (meth) acrylate having a repeating unit of 1 to 50 And the like.

Specific examples of the isocyanate having three or more functional groups include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,12-diisocyanatodecane, (Isocyanatomethyl) cyclohexane, trans-1,4-cyclohexane diisocyanate, 4,4'-methylene (isocyanatoethyl) isocyanate, Bis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethyl xylene- Derived from isocyanate, 1, -chloromethyl-2,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenyl isocyanate), 4,4'-oxybis (phenylisocyanate), hexamethylene diisocyanate The trifunctional isocyanate or isophorone diisocyanate-derived trifunctional It may be a cyanate.

Specific examples of the polyfunctional alcohols include ethoxylated dipentaerythritol, propoxylated pentaerythritol and the like.

Specific examples of the acrylic isocyanate include 2- (meth) acryloyloxyethyl isocyanate, 2-isocyanatoethyl acrylate, and the like.

The preferred molar number of addition of at least one selected from the group consisting of ethylene oxide and propylene oxide to be added to the photopolymerizable compound according to the present invention is 2 to 10 moles. When the addition mole number of the moiety is less than 2 moles, the development speed of the photosensitive resin composition may be lowered. When the addition mole number of the oxide is more than 10 moles, the curing rate is lowered and the curing density is lowered and the surface hardness, And the like may be deteriorated. In the polyfunctional monomer represented by the above formula (1), the urethane bond may be contained at any position in the molecule but is preferably included in the main chain. In addition, the number of acrylic functional groups in the polyfunctional monomer represented by Formula 1 is not particularly limited, but it is more preferable that the acrylic functional groups are included in a part or end of the main chain in the number of 3 to 12.

The photopolymerizable compound may be selected from pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate , Trimethylolpropane tri (meth) acrylate, and the like.

The content of the photopolymerizable compound may be 1 to 60% by weight, preferably 5 to 50% by weight based on 100% by weight of the total of the alkali-soluble resin and the photopolymerizable compound to be described later. When the photopolymerizable compound is contained within the above range, there is an advantage that the development speed is fast and no development residue is generated.

coloring agent

Rhodamine-based dye

The colored photosensitive resin composition according to an embodiment of the present invention includes a colorant containing a rhodamine-based dye present in a particulate state.

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 >

Since the colored photosensitive resin composition according to an embodiment of the present invention includes a rhodamine-based dye present in a particle state, there is an advantage of improving the brightness of a color filter substrate when a color filter is manufactured.

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 ₅ 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 ₆ R ₇ group,

R ₆ and R ₇ 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 an embodiment of the present invention may further include at least one selected from the group consisting of an alkali-soluble resin, a photopolymerization initiator, 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- .

Light curing Initiator

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

The photopolymerization initiator can be used without any particular limitation as long as it is used in the art as a photopolymerization initiator, but it preferably contains at least one selected from the group consisting of a triazine-based compound, an acetophenone-based compound, a nonimidazole-based compound and an oxime compound Do. When the colored photosensitive resin composition contains the photopolymerization initiator, the sensitivity is improved and the strength and patterning property of the pixel portion of the pixel pixel formed using the photopolymerizable composition are improved.

In addition, when a photopolymerization initiator is used in combination with a photopolymerization initiator, the photosensitive resin composition containing the photopolymerization initiator becomes more sensitive, and the productivity when the color filter is formed using the composition can be improved.

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 nonimidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group at the 4,4', 5,5 ' An imidazole compound substituted by a carboalkoxy 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.

Specific examples of the photopolymerization initiator other than the photopolymerization initiator described above include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These may be used alone or in combination of two or more.

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 also be used as photopolymerization initiators.

As the photopolymerization initiator which can be used in combination with the photopolymerization initiator in the present invention, one or more compounds selected from the group consisting of an amine compound and a carboxylic acid compound can be preferably used.

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, 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- ) Benzophenone, and the like. As the amine compound, an aromatic amine compound is 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, dichloro And aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The content of the photopolymerization initiator is preferably 0.1 to 20% by weight, more preferably 1 to 12% by weight based on 100% by weight of the total solid content of the colored photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, the colored photosensitive resin composition containing the photopolymerization initiator is highly sensitized, so that the strength of the pixel portion and the smoothness on the surface of the pixel portion can be excellent.

The content of the photopolymerization initiator is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on 100% by weight of the total solids of the colored photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, the sensitivity of the colored photosensitive resin composition containing the photopolymerization initiator is further increased, and the productivity of the color filter formed using the composition can be improved.

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 thermally curing 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: Ethylene Oxide  Additional Trifunctional  The compound (B-1)

(0.22 mol) of isocyanurate type oligomer of hexamethylene diisocyanate (Bayer, N3300), polyethylene glycol monoacrylate (Cognis Co., Ltd.), and a mixture of ethylene glycol monoacrylate 271.4 parts by weight (0.81 mole) of biscompound PEA6, and 0.1 part by weight of methoxyhydroquinone (Eastman, HQMME) were added and stirred at room temperature. The reaction was terminated after confirming that the isocyanate characteristic peak of 2260 cm ^-1 completely disappeared after 4 hours from the initiation of the reaction until the reaction temperature reached 105 ° C. and measuring by FT-IR.

Synthetic example  4: Ethylene Oxide  Additional 6 sensation  The compound (B-2)

In a 0.5 L three-necked reactor equipped with a mechanical stirrer, a thermometer and a condenser tube, 282.24 parts by weight (2 mol) of 2-isocyanatoethyl acrylate (AOI-VM, manufactured by Showa Denko K.K.), ethoxylated dipentaerythritol , 103.66 parts by weight (0.2 mol) of methoxyhydroquinone (Sigma-aldrich, CAS 30599-15-6) and 0.2 parts by weight of methoxyhydroquinone (Eastman, HQMME) were added and stirred at room temperature. Self-heating was performed until the reaction temperature reached 105 DEG C, and after 6 hours, FT-IR measurement was carried out to confirm that the isocyanate characteristic peak 2260 cm &lt; ^-1 &gt; completely disappeared and the reaction was terminated.

Synthetic example  5: 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 stand for 2 hours while maintaining the temperature at 90 占 폚. After 1 hour, the temperature was elevated to 110 占 폚 and maintained for 3 hours. A gas introduction tube was then introduced to prepare an oxygen / nitrogen mixed gas of 5 / Of 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 5, 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 placed in a mayonnaise bottle having a volume of 140 ml and kneaded at 60 DEG C for 10 hours by a paint conditioner to carry out dispersion 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 - 12 - - - - A-2 - 12 - 12 - - 12 - - A-3 - - - - - 12 - 12 - A-4 - - - - - - - - 12 Photopolymerizable compound B-1 8 8 - - - 8 - - 8 B-2 - - 8 8 10 - - - - B-3 - - - - - - 8 8 - Alkali-soluble resin C 8 8 8 8 6 8 8 8 8 Photopolymerization initiator D 3 3 3 3 3 3 3 3 3 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: Trifunctional compound to which ethylene oxide was added in Synthesis Example 3
B-2: 6-functional compound to which ethylene oxide was added in Synthesis Example 4
B-3: dipentaerythritol hexaacrylate (KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.)
C: 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, and polystyrene reduced weight average molecular weight was 20,000)
D: Irgacure OXE02 (manufactured by BASF)
E: Propylene glycol monomethyl ether acetate
F: SH-8400 (manufactured by Dow Corning)

Experimental Example

Experimental Example  1: Measurement of luminance

The solution of the colored photosensitive resin compositions of the above Examples and Comparative Examples was coated on a glass substrate, and then the resultant was pre-treated by baking on a hot plate at 90 DEG C for 3 minutes, and a test photomask having a circular pattern with a diameter of 1 mu m to 50 mu m was placed And the distance between the test photomask and the test photomask was set to 100 탆. At this time, the ultraviolet light source was irradiated at 100 mJ / cm ² using 1 kw high pressure mercury lamp containing g, h and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed with a KOH aqueous solution developing solution having a pH of 10.5, and post-baked at 230 ° C for 20 minutes. The transmittance chromaticity was measured at X, Y, and Z coordinate axes at a C light source of 2 °, and the Y value at this time was measured using a luminance meter (CM-3700d, Konica Minolta Sensing Co., Ltd.) . 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  2: Heat resistance measurement

The solution of the colored photosensitive resin compositions of the above Examples and Comparative Examples was coated on a glass substrate, and then the resultant was pre-treated by baking on a hot plate at 90 DEG C for 3 minutes, and a test photomask having a circular pattern with a diameter of 1 mu m to 50 mu m was placed And the distance between the test photomask and the test photomask was set to 100 탆. At this time, the ultraviolet light source was irradiated at 100 mJ / cm ² using 1 kw high pressure mercury lamp containing g, h and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed with a KOH aqueous solution developing solution having a pH of 10.5, and post-baked at 230 ° C for 20 minutes. The color filter manufactured later was further baked at 230 DEG C for 2 hours to compare the color change before and after the baking. The color filter was set in a spectroscopic colorimeter (CM-3700d, manufactured by Konica Minolta Sens 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 *, and b * is calculated by Equation (1), and the more reliable the color filter is, the smaller the color change value is. The results are shown in Table 2 below.

[Equation 1]

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

Experimental Example  3: Development speed measurement

The colored photosensitive resin composition solutions of the above-mentioned Examples and Comparative Examples were coated on the organic substrate, and then the resultant was pre-treated by baking on a hot plate at 90 DEG C for 3 minutes, and a test photomask having a circular pattern of a diameter of 1 mu m to 50 mu m was placed And the distance between the test photomask and the test photomask was set to 100 탆. At this time, the ultraviolet light source was irradiated at 100 mJ / cm ² using 1 kw high pressure mercury lamp containing g, h and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed with a KOH aqueous solution developing solution having a pH of 10.5. The minimum development time at which pattern formation was possible and no residue was left in the unexposed area was measured at the developing speed, and the results are shown in Table 2 below.

Experimental Example  4: Phenomenon Residue  Measure

The colored photosensitive resin compositions prepared in Examples and Comparative Examples were applied to a glass having a size of 5 x 5 cm, dried, and then coated to a thickness of 2.5 mu m. Thereafter, the resultant was dried in an oven at 100 ° C for 5 minutes to remove the solvent, and then immersed in a KOH aqueous solution having a pH of 10.5 for 1 minute, and then taken out and observed with a surface inspection lamp (FR-100R) The results are shown in Table 2 below.

<Evaluation Criteria>

<Evaluation Criteria>

○: no residual surface resin is observed at all

DELTA: Surplus of the surface resin is visually recognized, but slightly visible.

&Lt; / RTI &gt; &lt; RTI ID = 0.0 &gt; x: &lt; / RTI &gt;

Luminance Heat resistance Development speed Residue Example 1 1.12 1.21 15 ○ Example 2 1.08 1.23 16 ○ Example 3 1.1 1.31 10 ○ Example 4 1.07 1.33 8 ○ Example 5 1.09 1.32 5 ○ Comparative Example 1 One 3.55 17 △ Comparative Example 2 1.07 2.14 30 × Comparative Example 3 0.95 3.67 36 × Comparative Example 4 0.6 1.36 15 ○

Referring to Table 2 above, Examples 1 to 5 of the present invention, which include both a colorant containing a rhodamine-based dye in a particle state, a dispersing agent containing a triazine-based compound, and a photopolymerizable compound containing an ethylene oxide- Comparative Example 1 in which a dispersant containing a triazine-based compound is not contained; And Comparative Examples 2 to 3 which did not contain a photopolymerizable compound containing a compound added with ethylene oxide; It was confirmed that both the luminance, the heat resistance, and the developability were superior, and that the luminance was superior to that of Comparative Example 4 which did not contain the rhodamine-based dye.

Claims (9)

A photopolymerizable compound having at least one moiety selected from the group consisting of oxyethylene and oxypropylene in the molecular structure and having a trifunctional or higher urethane acrylic structure or a structural analog thereof;
A colorant comprising a rhodamine-based dye in a particulate state; And
And a dispersing agent containing a triazine compound. 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 photopolymerization initiator, a solvent, and an additive. The method according to claim 1,
The colored photosensitive resin composition according to claim 1,
[Chemical Formula 1]

(In the formula 1,
R &lt; ₁ &gt; is selected from the group consisting of hydrogen and a methyl group,
R &lt; ₂ &gt; are each independently selected from the group consisting of hydrogen and methyl groups,
R ₃ is selected from the group consisting of -NHCOO-, -COONH-, -NHCONH-, -NHCOS- and -SCONH-,
R &lt; ₄ &gt; is selected from the group consisting of an aliphatic alkyl having 3 to 50 carbon atoms, an unsaturated alkyl, a cycloalkyl and an aromatic group,
m is an integer of 3 to 12, and n is an integer of 1 to 10). The method according to claim 1,
Wherein the photopolymerizable compound is contained in an amount of 1 to 60% by weight based on 100% by weight of the total of the alkali-soluble resin and the photopolymerizable compound. 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, 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,
Wherein the triazine-based compound is represented by the following formula (2): &lt; EMI ID =
(2)

(In the formula (2)
R ₅ 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 ₆ R ₇ group,
R ₆ and R ₇ 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). A color filter comprising a cured product of the colored photosensitive resin composition according to any one of claims 1 to 7. An image display apparatus comprising the color filter of claim 8.