KR20100104189A - Color filter and liquid crystal display device having the same - Google Patents

Abstract

PURPOSE: A color filter and a liquid crystal display device including the same are provided to prevent the deterioration of brightness and afterimage. CONSTITUTION: A color filter comprises a coloration layer on a substrate arranged on a thin film transistor. The coloration layer is made of color sensitive resin composite. The coloration layer includes a coloration material(a), a bonding agent resin(b), a photopolymerization compound(c), a photopolymerization initiator(d) and a solvent(e). The coloration material includes a C.I. pigment green 58 and a C.I. pigment yellow 138. The bonding agent resin includes a copolymer obtained by a copolymerization reaction.

Description

COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE HAVING THE SAME}

The present invention relates to a color filter including a colored layer formed using a colored photosensitive resin composition on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, and a liquid crystal display device having the same.

In a color liquid crystal display device using a thin film transistor (TFT) substrate, conventionally, a color filter substrate for displaying a color image is manufactured separately from a driving substrate on which a thin film transistor (TFT) is disposed, and the color filter substrate is described above. It was manufactured by bonding to a driving substrate. However, in this system, since the positional accuracy at the time of joining is low, the width | variety of a black matrix must be enlarged and it is difficult to raise aperture ratio (namely, the ratio of the opening which permeate | transmits light).

On the other hand, with respect to the above method, a colored layer is formed directly on the surface of the driving substrate on which the thin film transistor (TFT) is arranged or on a protective film such as a silicon nitride film, and the substrate on which the colored layer is formed is sputtered by ITO (Indium). A method of bonding to a substrate on which a tin oxide electrode or an indium zinc oxide (IZO) is formed has been developed.

In this method, since a colored layer including a pixel or a black matrix is formed directly on the driving substrate, the bonding process between the color filter substrate and the driving substrate is unnecessary, and the aperture ratio can be greatly improved as compared with the former method. It is possible to obtain a bright and high precision display device.

In addition, the colored layer formed by such a method requires the formation of an electrical hole by dry etching in order to conduct the common electrode disposed on the colored layer and the driving substrate terminal under the colored layer. And a conductive path, such as a rectangular through hole or a U-shaped recess, having a length of about 1 to 30 µm, preferably 5 to 20 µm or less.

In this case, when using a colored radiation-sensitive composition used to form a colored layer on a driving substrate of a conventional thin film transistor (TFT) type color liquid crystal display device, the dry etching is performed after dry etching. Since there is a problem that the luminance is lowered due to the metal component due to the pigment around the electrical contact hole (Contact Hole) is performed, a solution for this has been required.

SUMMARY OF THE INVENTION An object of the present invention is to provide an afterimage due to a pigment component due to excellent chemical stability when forming a contact hole between a pixel electrode and an active element (TFT) in a color filter on array (COA) structure. It is providing the color filter containing the colored layer formed using the coloring photosensitive resin composition from which brightness fall does not occur.

Another object of the present invention is to provide a liquid crystal display device having the color filter.

In order to achieve the above object, the present invention provides a C.I. Pigment Green 58 and C.I. Colored layer formed using the coloring photosensitive resin composition containing the coloring material (A) containing pigment yellow 138, binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E). It provides a color filter comprising a.

In order to achieve another object of the present invention, the present invention provides a liquid crystal display device characterized in that the color filter according to the present invention is provided.

The color filter according to the present invention comprises a colored layer formed by using a colored photosensitive resin composition containing a coloring material, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, and in particular, C.I. Pigment Green 58 and C.I. By using Pigment Yellow 138 in combination, the chemical stability is excellent even if dry etching is performed, and thus, afterimage and luminance reduction do not occur. Therefore, the color filter according to the present invention can be preferably applied to the liquid crystal display device in the electronic industry.

Hereinafter, the present invention will be described in detail.

The color filter which concerns on this invention is colored photosensitive containing a coloring material (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E) on the board | substrate with which the thin film transistor was arrange | positioned. The colored layer formed using the resin composition is included.

Hereinafter, each component contained in the coloring photosensitive resin composition of this invention is demonstrated in detail.

Coloring material (A)

The coloring material (A) is C.I. Pigment Green 58 and C.I. Pigment yellow 138. Thus, as a coloring material (A), C.I. Pigment Green 58 and C.I. When Pigment Yellow 138 is included, even after dry etching, the chemical stability is excellent, and thus afterimage and luminance deterioration do not occur.

C.I. in the coloring material (A). Pigment Green 58 and C.I. The content of Pigment Yellow 138 is preferably 5 to 60% by mass and 0.1 to 50% by mass, more preferably 10 to 50% by mass, based on the mass fraction of the solids in the colored photosensitive resin composition. C.I. in the coloring material (A). Pigment Green 58 and C.I. When the content of pigment yellow 138 is 5 to 60% by mass and 0.1 to 50% by weight based on the above criteria, dry etching may be performed even after the formation of the contact hole by dry etching. It is preferable because there is little metal remaining in the surroundings and thus no afterimage occurs.

The coloring material (A) includes the C.I. Pigment Green 58 and C.I. Pigments other than Pigment Yellow 138 may be used. The content of the other pigment is generally 50% by mass or less, preferably 40% by mass or less, based on the mass fraction of the pigment component of the colored photosensitive resin composition. The expression "other pigments" herein refers to C.I. Pigment Green 58 and C.I. Pigment other than pigment yellow 138.

As another pigment which can be used in the said coloring material (A), the compound specifically classified as a pigment in the color index (The society of Dyers and Colourists) is mentioned, More specifically, the color index (the following) ( Although pigment of CI) number is mentioned, it is not necessarily limited to these.

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

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

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

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

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

C.I. Pigment Green 7, 10, 15, 25, 36 and 47

C.I. Pigment Brown 28

C.I. Pigment Black 1 & 7 etc

These coloring materials (A) can be used individually or in combination of 2 or more types, respectively.

At this time, the color filter of the present invention as the coloring material (A) C.I. Pigment Red 254, C.I. Pigment Red 242 or C.I. Pigment Red 177 may be formed using a colored photosensitive resin composition containing at least one selected from the group consisting of.

Pigment Red 254, C.I. Pigment Red 242 or C.I. The at least one content selected from the group consisting of Pigment Red 177 is 5 to 60% by mass, preferably 10 to 50% by mass, based on the mass fraction of the solids in the colored photosensitive resin composition. Pigment Red 254, C.I. Pigment Red 242 or C.I. When at least one content selected from the group consisting of Pigment Red 177 is contained within the above range on the basis of the above reference, dry etching may be performed even after the formation of a contact hole by a dry etching method when forming red pixels. Dry Etching) It is preferable because there is less metal remaining in the vicinity, so that no afterimage occurs. The content of the coloring material (A) is 5 to 60% by mass, preferably 10 to 50% by mass, based on the mass fraction with respect to the solid content in the colored photosensitive resin composition. When the coloring material (A) is contained within the above range, a sufficient color density can be ensured, and since a good pattern can be formed, the coloring material (A) is preferably contained within the above range.

Solid content in a coloring photosensitive composition in this invention means the sum total of the component remove | excluding the solvent.

When the coloring material is a pigment, the pigment dispersion liquid of the state in which the pigment was disperse | distributed uniformly in the solution can be obtained by containing a pigment dispersing agent and performing a dispersion process.

As the pigment dispersant, for example, cationic, anionic, nonionic, amphoteric, polyester-based, and polyamine-based, polyacrylic-based surfactants can be used, and these may be used alone or in combination of two or more thereof. Can be used.

When using a pigment dispersant, the usage-amount is per 1 mass part of coloring materials in a coloring photosensitive resin composition, Preferably it is 1 mass part or less, More preferably, it is 0.05 mass part-0.5 mass part. When the usage-amount of a pigment dispersant exists in the said range, since the pigment of a uniform dispersion state is obtained, it is preferable to use a pigment dispersant within the said range.

Binder Resin (B)

It is preferable that the said binder resin (B) contains the copolymer obtained by the copolymerization reaction containing the compound (B1) represented by following formula (1).

<Formula 1>

Wherein n is 0 or 1, R1 and R2 are each independently hydrogen or an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 12 carbon atoms, and R3, R4, R5 and R6 are each And thus each independently hydrogen, an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 30 carbon atoms, and two selected from R 3, R 4, R 5, and R 6 are linked or unbranched branches.

The hetero atom may be present in the main skeleton or in a branch, and may exist in the form of a carbonyl group, an ether group, an alcohol group, an amine group, a heterocycle, and the like, and is not limited.

The binder resin (B) usually has reactivity and alkali solubility due to the action of light or heat and acts as a dispersion medium of the coloring material.

The binder resin (B) contained in the coloring photosensitive resin composition of this invention is an unsaturated group containing resin containing the structural unit which can be obtained by superposition | polymerization (this is also a concept including copolymerization) of the compound represented by the said Formula (1) The binder resin of one embodiment according to the invention is preferably a copolymer obtained by a copolymerization reaction comprising the compound of formula 1 (B1), a compound having a unsaturated bond (B2) and a compound having a carboxyl group and an unsaturated bond (B3). It is more preferable that it is unsaturated group containing resin obtained by making the said copolymer obtained by making the compound (B4) which has an unsaturated bond and an epoxy group further react in 1 molecule.

In one embodiment of the present invention, the compound (B1) of the general formula (1) may be included in at least one selected from the compound having a structural formula of the formula 2 to 17 more specifically.

Compound (B1) represented by the formula (1) according to the present invention is not limited to the structure of the formula (2) to 17 and all derivatives or all derivatives of the compound of the formula (1) including the norbornene skeleton structure is included in the present invention. These can be used individually or in combination of 2 types or more, respectively.

In addition, the (meth) acrylate recorded in this specification means an acrylate and / or a methacrylate.

In one embodiment of the present invention, the compound (B2) having an unsaturated bond is not limited as long as it is a compound having an unsaturated double bond that can be polymerized. Specific examples thereof include methyl (meth) acrylate and ethyl (meth). Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate, cyclopentyl (meth) acrylate , Cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, Cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, iso Unsaturated carboxyl containing alicyclic substituents, such as carbonyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pineneyl (meth) acrylate Substituents which have aromatic rings, such as monosaturated carboxylic acid ester compound of glycols, such as an acid ester compound and oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, Aromatic vinyl compounds, such as an unsaturated carboxylic acid ester compound, styrene, (alpha) -methylstyrene, and vinyltoluene containing, carboxylic acid vinyl esters, such as vinyl acetate and a vinyl propionate, (meth) acrylonitrile, (alpha)-chloro acrylonitrile Maleimide compounds, such as vinyl cyanide compounds, N-cyclohexyl maleimide, and N-phenyl maleimide, etc. are mentioned. These can be used individually or in combination of 2 types or more, respectively.

In one embodiment of the present invention, the compound (B3) having an unsaturated bond with the carboxyl group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond capable of polymerization, and specific examples thereof include acrylic acid and methacrylic acid. have. Acrylic acid and methacrylic acid can be used individually or in combination of 2 types or more, respectively. In addition to these acrylic acid and methacrylic acid, one or more other acids may be used. As another acid, it is also possible to specifically use together the carboxylic acid chosen from 1 type or more of other unsaturated carboxylic acids, such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. Moreover, you may use together the monomer containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid.

In one embodiment of the present invention, in the copolymer obtained by copolymerizing (B1) to (B3) used in the present invention (even when monomers other than B1 to B3 are further included and copolymerized, they are included in the present invention). , And the proportion of the constituents derived from each of (B1) to (B3) is preferably in the following ranges in mole fraction with respect to the total moles of the constituents constituting the copolymer.

Structural unit derived from (B1): 2 to 30 mol%,

Structural unit derived from (B2): 2 to 95 mol%,

Structural units derived from (B3): 2 to 70 mol%

That is, the copolymer obtained by the copolymerization reaction containing the compound (B1) of the said General formula (1), the compound (B2) which has an unsaturated bond, and the compound (B3) which has a carboxyl group and an unsaturated bond is respectively (B1)-(B3) Regarding the total moles of constituents derived from the monomers of Formula 1, the monomer having an unsaturated bond, and the unsaturated carboxylic acid monomer are included in the range of 2 to 30 mol%, 2 to 95 mol%, and 2 to 70 mol%, respectively. It is preferable to be.

In particular, it is more preferable that the ratio of the structural component derived from each of said (B1)-(B3) is the following ranges with respect to the total mole number of the said copolymer structural component.

Structural unit derived from (B1): 5-30 mol%,

Structural unit derived from (B2): 5 to 80 mol%,

Structural units derived from (B3): 5-65 mol%

As described above, when the ratio of the constituents derived from each of (B1) to (B3) is in the above range, the balance of developability, solubility and heat resistance is good, so that a preferable copolymer can be obtained.

In one embodiment of the present invention, as an example of the production method of the copolymer, when copolymerized (B1) to (B3) is obtained by copolymerization can be produced by copolymerizing in the following method.

Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube, 0.5 to 20 times the amount of solvent was introduced together with respect to the total mass of (B1) and (B1) to (B3) in a flask. The atmosphere is replaced with nitrogen in air. Then, after heating up a solvent at 40-140 degreeC, 0-20 times of a solvent by mass basis with respect to the predetermined amount of (B2) and (B3), and the total mass of (B2)-and (B3), and azo A solution in which a polymerization initiator such as bisisobutyronitrile or t-butylperoxy 2-ethylhexyl carbonate is added at a molar fraction of 0.1 to 10 mol% based on the total number of moles of (B1) to (B3) (stirring at room temperature or heating Dissolution) is added dropwise to the flask from 0.1 dropping lot over 0.1 to 8 hours, and further stirred at 40 to 140 ° C for 1 to 10 hours.

In the above process, part or all of the polymerization initiator may be put in the flask, or part or all of (B1) to (B3) may be put in the flask. The remaining amount can be added during polymerization with (B4).

As the solvent used in the above process, a solvent used in a normal radical polymerization reaction may be used, and specifically, tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether , Toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like. These solvents can be used alone or in combination of two or more thereof.

Moreover, as a polymerization initiator used for said process, the polymerization initiator normally used can be added, It does not restrict | limit in particular. Specifically, diisopropyl benzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxy isopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, t-butyl Organic peroxides such as peroxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitoryl), dimethyl 2,2'-azobis (2-methylpropionate), etc. And nitrogen compounds. These can be used individually or in combination of 2 types or more, respectively.

Moreover, in order to control molecular weight and molecular weight distribution in the said process, (alpha) -methylstyrene dimer and a mercapto compound can also be used as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005 to 5% by mass fraction with respect to the total mass of (B1)-(B3). In addition, the said polymerization conditions can also adjust an input method and reaction temperature suitably in consideration of the amount of heat generation by a manufacturing facility, superposition | polymerization, etc ..

Binder resin (B) contained in the coloring photosensitive resin composition which concerns on this invention can be obtained by making (B4) further react with the copolymer obtained by copolymerizing said (B1)-(B3). By adding (B4) to the copolymer, light / thermosetting property can be imparted to the binder resin.

In one Embodiment of this invention, As a specific example of the compound (B4) which has an unsaturated bond and an epoxy group in the said 1 molecule, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl (meth) acrylate, 3 And 4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate, and the like. Among these, glycidyl (meth) acrylate is preferably used. These can be used individually or in combination of 2 types or more, respectively.

It is preferable to make said (B4) react with 5 to 80 mol% in mole fraction with respect to the mole number of the component derived from (B3) in the said copolymer, Especially 10-80 mol% is good. When compound (B4) which has an unsaturated bond and an epoxy group exists in the said range, since sufficient photocurability and thermosetting are obtained, a sensitivity and pencil hardness are compatible, and it is excellent in reliability, and it is preferable.

In one embodiment of the present invention, the binder resin (B) can be produced by reacting a copolymer obtained by copolymerizing the above (B1) to (B3) and (B4) by, for example, the following method. .

When the copolymer of (B1) to (B3) is obtained by the method described above, the atmosphere in the flask is replaced with nitrogen to air, and the molar fraction is 5 in terms of the number of moles of the constituents derived from (B3) in the copolymer. 0.01 to 5% by mass and a polymerization inhibitor as the mass fraction of trisdimethylaminomethylphenol, for example, as a reaction catalyst of (B4) to 80 mol% of the carboxyl group and the epoxy group, based on the total mass of (B1) to (B4). For example, hydroquinone is added to 0.001 to 5% by mass in a flask at a mass fraction with respect to the total mass of (B1) to (B4), and reacted at 60 to 130 ° C for 1 to 10 hours, thereby allowing the copolymer and ( B4) can be reacted. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

In one embodiment of the present invention, the binder resin (B) preferably has a weight average molecular weight in terms of its polystyrene in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of binder resin (B) exists in the range of 3,000-100,000, film | membrane decrease does not occur at the time of image development, and since the missing property of a non-pixel part at the time of image development is preferable.

The acid value of the binder resin (B) is preferably in the range of 30 to 300 mgKOH / g based on solid content. If the acid value is less than 30 mgKOH / g, there is a possibility that the developability to alkaline water is lowered and residues remain on the substrate, and when the acid value exceeds 300 mgKOH / g, the possibility of desorption of the pattern increases.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (B), it is more preferable that it is 1.8-4.0. Since molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5-6.0, since developability is excellent, it is preferable.

Content of binder resin (B) is 5-90 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it is the range of 10-70 mass%. When the content of the binder resin (B) is 5 to 90% by mass based on the above criteria, the solubility in the developing solution is sufficient, and development residues are less likely to occur on the substrate of the non-pixel portion, and the film reduction of the pixel portion of the exposed portion at the time of development is reduced. Since it is hard to produce and the omission property of a non-pixel part is favorable, it is preferable.

Photopolymerizable Compound (C)

The said photopolymerizable compound (C) is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl py. A ralidone etc. are mentioned.

As a specific example of the said bifunctional monomer, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate And bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of the other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaeryte Lithol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, bifunctional or higher polyfunctional monomers are preferably used.

The photopolymerizable compound (C) is used in a mass fraction of 1 to 60% by mass, preferably 5 to 50% by mass, based on the solid content in the colored photosensitive resin composition. If the photopolymerizable compound (C) is in the range of 1 to 60% by mass based on the above criteria, the intensity and smoothness of the pixel portion will be good, and thus it is preferable.

Photopolymerization Initiator (D)

Although the said photoinitiator (D) is not restrict | limited, It is preferable to use at least 1 sort (s) of compound chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound. The coloring photosensitive resin composition containing said photoinitiator (D) is highly sensitive, and the film | membrane formed using this composition becomes favorable the intensity | strength and surface smoothness of the pixel part.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Moreover, as said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] Oligomer of propan-1-one, etc. are mentioned.

Moreover, as an acetophenone type compound which can be used other than said acetophenone type compound, the compound represented by following formula (18) is mentioned, for example.

&Lt; Formula 18 >

In Formula 18, R1 to R4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, a benzyl group or carbon number which may be substituted by an alkyl group having 1 to 12 carbon atoms. The naphthyl group which may be substituted by the alkyl group of 1-12 is shown.

Specific examples of the compound represented by Formula 18 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one and 2-ethyl-2-amino (4-morpholinophenyl) ethane- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl- 2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholin Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-, for example) Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, and a phenyl group at the 4,4', 5,5 'position is carbo The imidazole compound substituted with the alkoxy group etc. are mentioned. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole or 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compound include 0-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one or compounds represented by the following formulas (19) to (21).

<Formula 19>

<Formula 20>

<Formula 21>

Moreover, as long as it does not impair the effect of this invention, the photoinitiator of this invention can also use together another photoinitiator etc. which are normally used in this field.

As said other photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

In addition to 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone and methyl phenyloxyoxylate , A titanocene compound, etc. are mentioned as another photoinitiator.

In addition, you may use combining a photoinitiator (D-1) with the said photoinitiator (D). When photopolymerization start adjuvant (D-1) is used together with the said photoinitiator (D), since the coloring photosensitive resin composition containing these becomes more sensitive and the productivity at the time of forming a color filter using this composition is preferable, it is preferable.

As said photopolymerization start adjuvant (D-1), an amine compound and a carboxylic acid compound are used preferably.

Specific examples of the amine compound in the photopolymerization start adjuvant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4'- Aromatic amine compounds, such as bis (diethylamino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.

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

The amount of the photopolymerization initiator (D) used in the colored photosensitive resin composition of the present invention is 0.1 to 40 mass%, preferably in a mass fraction, based on the total mass of the binder resin (B) and the photopolymerizable compound (C). It is 1-30 mass%, and the usage-amount of a photoinitiator adjuvant (D-1) is 0.1-50 mass% in mass fraction with respect to the total mass of binder resin (B) and a photopolymerizable compound (C) based on solid content, Preferably Is 1-40 mass%. When the usage-amount of a photoinitiator (D) exists in the said range, since the coloring photosensitive resin composition becomes high sensitivity, since the intensity | strength of the pixel part formed using this composition and the smoothness in the surface of this pixel part become favorable, it is preferable. Moreover, when the usage-amount of the said photoinitiator adjuvant (D-1) exists in the said range, since the sensitivity of a coloring photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition improves, it is preferable.

Solvent (E)

The said solvent (E) is not specifically limited, Various organic solvents used in the field of colored photosensitive resin composition can be used.

Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol Alkylene glycol alkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate and methoxy pentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, Ketones such as cetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3-meth Ester, such as methyl oxypropionate, Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Among the solvents (E), organic solvents having a boiling point of 100 to 200 ° C in the solvents are preferable from the viewpoint of applicability and drying properties, and more preferably alkyleneglycol alkylalkyl acetates, ketones, 3 Esters such as ethyl ethoxypropionate and methyl 3-methoxypropionate; and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone and ethyl 3-ethoxypropionate. And methyl 3-methoxypropionate. These solvents (E) can be used individually or in mixture of 2 or more types, respectively.

Content of the solvent (E) in the coloring photosensitive resin composition of this invention is 60-90 mass% normally with a mass fraction with respect to the coloring photosensitive resin composition whole quantity containing it, Preferably it is 70-85 mass%. When the content of the solvent (E) is in the range of 60 to 90% by mass based on the above criteria, it is applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. Since applicability | paintability becomes favorable at the time, it is preferable.

Additive (F)

The coloring photosensitive resin composition of this invention is a filler, another high molecular compound, a hardening | curing agent, and a pigment dispersant as needed. It is also possible to use additives (F) such as adhesion promoters, antioxidants, ultraviolet absorbers and anti-agglomerates in combination.

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

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be.

The said hardening | curing agent is used in order to raise core hardening and mechanical strength, An epoxy compound, an oxetane compound, etc. are mentioned as a hardening | curing agent.

Examples of the epoxy compound in the curing agent include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, noblock type epoxy resins and other aromatic epoxy resins and alicyclic compounds. Epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, Isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate and the like.

Examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane and cyclohexane dicarboxylic acid bis oxetane. .

The curing agent may include a curing aid compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound with the curing agent. As a hardening auxiliary compound, polyhydric carboxylic anhydrides are mentioned, for example.

As said polyhydric carboxylic anhydride, what is marketed as an epoxy resin hardener can be used. As this epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industries Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) are mentioned, for example. (Manufactured by Nippon Ewha Co., Ltd.). The said hardening | curing agent can be used individually or in mixture of 2 or more types.

Commercially available surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, Polyethyleneimines and the like, and other trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega MEGAFAC (made by Dainippon Ink & Chemicals Co., Ltd.), Florad (made by Sumitomo 3M Co., Ltd.), Asahi guard, Suflon (above, manufactured by Asahi Glass Co., Ltd.), Sol SLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptoprofil Trimethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned.

These adhesion promoters can be used individually or in combination of 2 or more types, respectively. It is 0.01-10 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it contains 0.05-2 mass%.

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

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

Specific examples of the aggregation inhibitor include sodium polyacrylate.

The coloring photosensitive resin composition of this invention mentioned above can be manufactured, for example by the following methods. The coloring material (A) is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 µm or less. Under the present circumstances, a pigment dispersant is used as needed and one part or all part of binder resin (B) may be mix | blended. The remainder of binder resin (B), the photopolymerizable compound (C) and the photoinitiator (D), the other components used as needed, and the additional solvent as needed in the obtained dispersion liquid (henceforth a mill base). It can further add so that it may become a predetermined density | concentration, and can obtain the target coloring photosensitive resin composition. However, the present invention does not limit this method.

The color filter according to the present invention includes a colored layer prepared by using the colored photosensitive resin composition having the above-described composition. FIG. 1 shows a manufacturing process of the color filter including the colored layer using the colored photosensitive resin composition of the present invention. It demonstrates using below.

When manufacturing a color filter by COA (Color Filter on Array) method using the coloring photosensitive resin composition which concerns on this invention, each pixel pattern of red, green, and blue is directly formed in the TFT layer substrate in which the SiNx (protective layer) coating film was formed. Is formed on the SiNx coating film (FIG. 1A).

In the process for forming an electrically conductive path between the TFT layer and the electrode (IZO layer), the positive photosensitive resin film is patterned using the mask to remove the SiNx (protective layer) coating film (FIG. 1B).

An electrically conductive path is formed by dry etching (dry etching) the SiNx (protective layer) located on the lower surface (electrically conductive path) of the positive photosensitive resin film (FIG. 1C).

Even when dry etching is performed in the manufacture of the color filter as described above, the colored photosensitive resin composition according to the present invention is excellent in chemical stability as it contains a specific pigment, and thus no afterimage and luminance decrease due to the pigment component are generated.

In order to remove the positive photosensitive resin film remaining on the pixel pattern of Fig. 1C, the positive photosensitive resin film layer is removed using a stripper developer (Fig. 1D).

An IZO layer to be used as a common electrode (IZO layer) with a TFT layer is deposited (FIG. 1E).

In order to form a common electrode (IZO layer) layer, a positive photosensitive resin film is formed on the IZO layer (FIG. 1F).

The exposed portion (the portion where the IZO layer is exposed) of the formed positive photosensitive resin film is removed by wet etching (wet etching) (FIG. 1G).

In order to remove the positive PR remaining on the common electrode (IZO layer) layer of FIG. 1G, the positive photosensitive resin film is removed using a stripper developer (FIG. 1H).

The color filter manufactured as described above is excellent in smoothness, and in particular, the afterimage and the luminance decrease due to the pigment do not occur. Therefore, when the color filter is applied to the liquid crystal display, an excellent quality liquid crystal display may be manufactured in high yield.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, embodiment of this invention disclosed below is an illustration to the last, and the scope of the present invention is not limited to these embodiment. The scope of the invention is indicated in the appended claims, and moreover contains all modifications within the meaning and range equivalent to those of the claims. In addition, "%" and "part" which show content in a following example and a comparative example mean the mass% or mass part with respect to a coloring photosensitive resin composition unless there is particular notice.

<Binder Resin Synthesis Example>

Synthesis Example 1 Resin (B-1)

Into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, 90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and 22.0 g of 2-norbornene (0.2 mol, 20 mol%) were mixed. The atmosphere in the flask was introduced into nitrogen from air, and after heating up to 80 ° C., 52.9 g (0.3 mol, 30 mol%) of benzyl methacrylate, 45.0 g (0.5 mol, 50 mol%) of methacrylic acid and propylene glycol To the mixture containing 136 g of monomethyl ether acetate, a solution obtained by adding 3.2 g of tert-butyroxy-ethylhexyl carbonate was added dropwise to the flask over 2 hours from the dropping lot, and the stirring was continued at 100 ° C. for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g of glycidyl methacrylate (0.2 mol (40 mol% based on the carboxyl group of methacrylic acid used in this reaction)), 0.9 g of trisdimethylaminomethylphenol, and hydroquinone 0.145 g was thrown into the flask, and reaction was continued at 110 degreeC for 6 hours, and resin B-1 whose solid acid value is 100 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 31,000, and molecular weight distribution (Mw / Mn) was 2.3.

At this time, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin were measured using an HLC-8120GPC (manufactured by Tosoh Corporation) apparatus, and the column was used by serially connecting TSK-GELG4000HXL and TSK-GELG2000HXL. The column temperature was 40 ° C, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 µl, and the detector RI was used, and the measurement sample concentration was 0.6 mass% (solvent = tetrahydrofuran), for calibration. TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) was used as a standard material.

Synthesis Example 2: Resin (B-2)

90 g of propylene glycol mono methyl ether acetate and 90 g of propylene glycol mono methyl ether were introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was nitrogen in air. A solution in which 3.2 g of terbutyrryloxy 2-ethylhexyl carbonate was added to a mixture containing 88.1 g (0.5 mol) of benzyl methacrylate, 45.0 g (0.5 mol) of methacrylic acid, and 136 g of propylene glycol mono methyl ether acetate. Was added dropwise to the flask over 2 hours from the dropping lot, and further stirring was continued at 100 ° C for 9 hours to obtain a resin B-2 having a solid acid value of 96 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 22,000, and molecular weight distribution (Mw / Mn) was 2.3.

At this time, the measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin was carried out under the same conditions as in Synthesis Example 1.

<Coloring Photosensitive Resin Compositions Preparation Examples 1 to 5 and Comparative Preparation Examples 1 to 7>

Among the components shown in Tables 1 and 2 below, a pigment as the coloring material (A), a pigment dispersant as other additives and a part of the propylene glycol monomethyl ether acetate as the solvent (E) are mixed beforehand, and the pigment is After sufficient dispersion, the bead mill was separated, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were further added and mixed to obtain a colored photosensitive resin composition.

Production Example Comparative Production Example One 2 3 One 2 3 4 5 Coloring material (A) C.I. Pigment Green 58 2.98 2.48 1.98 - - - 0.50 - C.I. Pigment Green 36 - - - 3.48 2.98 2.98 2.98 1.98 C.I. Pigment Yellow 138 0.50 1.00 1.50 - - 0.5 - 1.50 C.I. Pigment Yellow 150 - - - - 0.5 - - - Binder Resin (B) B-1 6.52 6.52 6.52 6.52 6.52 6.52 6.52 - B-2 - - - - - - - 6.52 Photopolymerizable
Compound (C) 4.35 Photopolymerization
Initiator (D) Initiator (D1) 1.96 Initiator (D2) 0.33 Solvent (E) 80.46 Additive (F) Additive (F1) 1.49 Additive (F2) 0.10

Production Example Comparative Production Example 4 5 6 7 Coloring material (A) C.I. Pigment Red 254 - 1.20 1.20 - C.I. Pigment Red 242 1.20 - - 1.20 C.I. Pigment Red 177 1.78 1.78 1.78 1.78 C.I. Pigment Yellow 138 0.50 0.50 - - C.I. Pigment Yellow 150 - - 0.5 0.5 Binder Resin (B) 6.52 Photopolymerizable
Compound (C) 4.35 Photopolymerization
Initiator (D) Initiator (D1) 1.96 Initiator (D2) 0.33 Solvent (E) 80.46 Additive (F) Additive (F1) 1.49 Additive (F2) 0.10

Photopolymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Initiator (D1): 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemical)

Initiator (D2): 4,4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Kagaku Co., Ltd.)

Solvent (E): propylene glycol monomethyl ether acetate

Additive (F1): Pigment Dispersant (Acrylic)

Additive (F2): 3-methacryloxypropyl trimethoxysilane

&Lt; Example 1 >

Using the colored photosensitive resin composition prepared in Preparation Example 1 to prepare a colored layer on a glass substrate as follows.

A 25 cm 2 glass substrate (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. An ITO electrode was deposited on the glass substrate at a thickness of 0.150 mu m. When the coloring photosensitive resin composition was exposed on the said board | substrate at 100 mJ / cm <2> exposure amount (365 nm), spin coating was carried out so that the film thickness after post-firing might be 3.0 +/- 0.5 micrometer when the image development process was skipped, and then in a clean oven, 100 Predrying was carried out for 3 minutes at ℃. After cooling, the substrate was coated with the colored photosensitive resin composition, and the interval between the quartz glass photomask (exposure section 30mm * 30mm) was set to 100 µm, and the atmosphere was made by using an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd. In the atmosphere, light irradiation was performed at an exposure dose (365 nm) of 100 mJ / cm 2. Thereafter, the coating film was immersed in a water-based developer containing 0.12% of nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C. for a predetermined time, and then washed with water in a 200 ° C. heating oven for 30 minutes after washing with a colored layer. Formed. The colored substrate made through the above method is subjected to dry etching under the same conditions using SF6 gas to etch about 30% of the coating film.

<Examples 2 and 3, Comparative Examples 1 to 5>

The same method as in Example 1 except for using the colored photosensitive resin composition prepared in Preparation Examples 2 and 3 and Comparative Examples 1 to 5, respectively, instead of using the colored photosensitive resin composition prepared in Preparation Example 1 on the substrate. Was carried out.

<Example 4>

In the same manner as in Example 1, except that the green and red pixel patterns were formed on the substrate using the colored photosensitive resin composition prepared in Preparation Example 1 and the colored photosensitive resin composition prepared in Preparation Example 4, respectively. Was carried out.

<Example 5>

In the same manner as in Example 1, except that the green and red pixel patterns were formed on the substrate using the colored photosensitive resin composition prepared in Preparation Example 1 and the colored photosensitive resin composition prepared in Preparation Example 5, respectively. Was carried out.

Comparative Example 6

Same as Example 1 except that the green and red pixel patterns were formed on the substrate using the colored photosensitive resin composition prepared in Comparative Preparation Example 1 and the colored photosensitive resin composition prepared in Comparative Preparation Example 6, respectively. It was carried out by the method.

&Lt; Comparative Example 7 &

Same as Example 1 except that the green and red pixel patterns were formed on the substrate using the colored photosensitive resin composition prepared in Comparative Preparation Example 1 and the colored photosensitive resin composition prepared in Comparative Preparation Example 7, respectively. It was carried out by the method.

Experimental Example

1. ICP-MS Evaluation

① After the installation of the Teflon ring (Teflon ring) on the specimen produced by the above method, NMP 0.5mL was added dropwise into the Teflon ring.

② left at room temperature for 15min.

③ After cooling NMP washed with DIW and diluting 20 times, ICP-MS was measured and the results are shown in Table 3 below.

At this time, the evaluation criteria for the metal content detected in the analysis as described above are as follows.

O for each metal element under 100ppb, X for over 100ppb.

Cu (ppb) Ni (ppb) Zn (ppb) Evaluation results Example 1 <20 <20 70 O Example 2 <20 <20 62 O Example 3 <20 <20 60 O Example 4 <20 <20 <20 O Example 5 <20 <20 <20 O Comparative Example 1 130 <20 <20 X Comparative Example 2 125 54 <20 X Comparative Example 3 135 <20 <20 X Comparative Example 4 129 39 <20 X Comparative Example 5 123 <20 <20 X Comparative Example 6 <20 105 <20 X Comparative Example 7 <20 110 <20 X

2. Light resistance and Outgas evaluation

2-1. Light resistance evaluation

① The specimen prepared by the above method was left for 240 hours under CCFL back light.

② Check the color difference ΔEab before and after standing and the results are shown in Table 4. The evaluation criteria for light resistance when analyzed by the above method is as follows.

O when ΔEab value is less than 2.0, X when 2.0 or more.

2-2. Outgas rating

① Outgas was analyzed by pyrolysis at 230 ° C. for 30 minutes through Py-GC / FID, and the results were shown in Table 4 below.

The evaluation criteria for Outgas when analyzed in the above manner is as follows.

The value of Comparative Example 5 was obtained as a percentage based on 100%. O if the percentage is less than 45%, X if the percentage is greater than 45%.

ΔEab Outgas Evaluation results Example 1 0.82 41% O Example 2 0.95 40% O Example 3 0.75 45% O Example 4 1.22 41% O Example 5 1.20 41% O Comparative Example 1 2.90 45% X Comparative Example 2 2.93 51% X Comparative Example 3 2.80 48% X Comparative Example 4 3.00 55% X Comparative Example 5 2.95 100% X Comparative Example 6 2.57 58% X Comparative Example 7 2.65 55% X

As shown in Table 3 and Table 4, in the case where the colored layer is formed using the colored photosensitive resin composition including the pigment according to the present invention, the chemical stability is superior to that of the comparative example, thereby providing a pixel electrode and an active element (TFT). When forming the contact hole (Contact Hole) of the metal component due to the pigment component can be confirmed that less than 100ppb is generated, accordingly, it can be seen that the afterimage and brightness reduction does not occur.

1 is a process chart of forming a colored layer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device using the colored photosensitive resin composition of the present invention.

&Lt; Brief Description of Drawings &

Ⓐ: pixel pattern of R / G / B ⓑ: SiNx <protective layer>

Ⓒ: TFT layer ⓓ: Glass substrate

Ⓔ: Positive PR ⓕ: IZO layer (common electrode)

Claims (6)

C.I. on the substrate on which the thin film transistor is disposed. Pigment Green 58 and C.I. The colored layer formed using the coloring photosensitive resin composition containing the coloring material (A) containing pigment yellow 138, binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E). Color filter, characterized in that it comprises. The method of claim 1, The colored layer is formed of C.I. Pigment Red 254, C.I. Pigment Red 242, or C.I. A color filter further comprising a pigmented photosensitive resin composition comprising at least one of pigment red 177. The method of claim 1, C.I. in the coloring material (A). Pigment Green 58 and C.I. The content of pigment yellow 138 is 5 to 60 mass% and 0.1 to 50 weight% in mass fractions with respect to the solid content in a coloring photosensitive resin composition, respectively. The method of claim 1, The said binder resin (B) is an unsaturated group containing resin obtained by making the following (B4) further react with the copolymer obtained by the copolymerization reaction containing the following (B1), (B2), and (B3) compound. filter: (B1): a compound represented by the following formula (1), <Formula 1>

(Wherein n is 0 or 1, R 1 and R 2 are each independently hydrogen or an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 12 carbon atoms, and R 3, R 4, R 5, and R 6 are positions) Are each independently hydrogen, an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 30 carbon atoms, and two of R 3, R 4, R 5, and R 6 are selected to be linked or unbranched.) (B2): a compound having an unsaturated bond copolymerizable with (B1) and (B3), (B3): a compound having a carboxyl group and an unsaturated bond (B4): A compound having an unsaturated bond and an epoxy group in one molecule. The method of claim 4, wherein In the binder resin (B), the proportion of the constituents derived from each of (B1) to (B3) is 2 to 30 mol% , Structural unit derived from (B2): 2 to 95 mol%, Structural unit derived from (B3): in the range of 2 to 70 mole%, The color filter characterized by reacting (B4) with 5-80 mol% with respect to the component derived from (B3). A liquid crystal display device comprising the color filter of claim 5.

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