KR102528890B1 - A black photo sensitive resin composition, a color filter comprising a black metrics and/or a column spacer prepared by using the composition, and a display comprising the color filter - Google Patents

Abstract

The present invention includes (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, wherein the (A) colorant is C.I. Providing a black photosensitive resin composition comprising Pigment Blue 15:3, a color filter including a column spacer, a black matrix, or a black column spacer manufactured using the same, and a display device including the color filter do.

Description

A black photosensitive resin composition, a color filter including a black matrix and/or column spacer manufactured using the same, and a display device including the color filter A COLUMN SPACER PREPARED BY USING THE COMPOSITION, AND A DISPLAY COMPRISING THE COLOR FILTER}

The present invention relates to a black photosensitive resin composition, a color filter including a black matrix and/or a column spacer manufactured using the same, and a display device including the color filter.

The color filter is composed of three primary color pixels of a red pixel, a green pixel, and a blue pixel, and a black matrix that is formed on the boundary between the respective color pixels and is black and does not substantially transmit visible light. The black matrix or black column spacer is a material that secures a space necessary for liquid crystal to move between two glass plates constituting the LCD and maintains the elasticity of the LCD, and is formed of a black photosensitive resin composition.

When the black photosensitive resin composition is used in a color filter of a liquid crystal display, a light blocking layer using the black photosensitive resin composition is formed at the boundary between the colored layers to enhance the contrast and color development of red, green and blue. In addition, recently, it is required to be positioned on an array substrate to form not only a role of a black matrix, but also a spacer for maintaining a cell gap so that various roles can be performed at once.

Black photosensitive resin composition is a material that is essential for color filters, liquid crystal display materials, organic light emitting devices, displays, etc. Research on black photosensitive resin composition with excellent elasticity and reliability as well as optical effect for basic light blocking is underway. is actively underway.

Korean Patent Registration No. 10-1658374 discloses a technique for improving the characteristics of a rack matrix, a barrier rib for an inkjet type color filter, and a spacer for a liquid crystal display by using a black photosensitive resin composition, and Korean Patent Publication No. 10-1658374 No. 2012-0033893 discloses a technology for improving the characteristics of a black matrix and a support spacer for maintaining a cell gap using a photosensitive resin composition, but has an advantage in optical characteristics because it contains a black pigment as an essential component, but has a reliability There is a problem with not being able to initiate enhancement.

Republic of Korea Patent No. 10-1658374 Republic of Korea Patent Publication No. 10-2012-0033893

The present invention is to provide a black photosensitive resin composition having excellent reliability and optical properties while improving the above problems.

In addition, the present invention is to provide a color filter including a column spacer, a black matrix, or a black column spacer manufactured using the black photosensitive resin composition.

In addition, the present invention is to provide a display device including the color filter.

The present invention includes (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, wherein the (A) colorant is C.I. A black photosensitive resin composition comprising Pigment Blue 15:3 is provided.

In addition, the present invention provides a color filter including a column spacer, a black matrix, or a black column spacer prepared using the colored photosensitive resin composition described above.

In addition, the present invention provides a display device including the color filter described above.

The present invention as a colorant C.I. Provided is a black photosensitive resin composition including Pigment Blue 15:3 and having improved reliability and optical properties.

In addition, the present invention provides a color filter and a display device including a column spacer, a black matrix or a black column spacer prepared by including the colored photosensitive resin composition.

The present invention includes (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, wherein the (A) colorant is C.I. A black photosensitive resin composition comprising Pigment Blue 15:3, a color filter including a black matrix and/or a column spacer manufactured using the same, and a display device including the color filter are provided.

The present invention may provide a black photosensitive resin composition having an optical density (OD) of 1.5 or more per 1 μm.

<Black photosensitive resin composition>

Hereinafter, each component constituting the black photosensitive resin composition of the present invention is described. However, the present invention is not limited by these components.

(A) colorant

The colorant is used to realize black, and imparts light blocking properties to all of the column spacer, the black matrix, and the black column spacer. The black column spacer means that the column spacer and the black matrix are integrally formed. That is, the black matrix serves to prevent light leakage, and the spacer can serve to prevent malfunction of the device due to external light.

The colorant is C.I. It is characterized by including Pigment Blue 15:3, and may include an orange colorant and a purple colorant, and in addition, all colorants known in the art may be used.

The C.I. Pigment Blue 15:3 (hereinafter, Blue 15:3) has excellent thermal stability due to molecular structure arrangement, and can exhibit better reliability and light characteristics in terms of solvent resistance compared to other blue colorants.

As the orange colorant, C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65 , 67, 69, 70, 71, 72, 73, 74, 75, 77, 78 and 79, and the like, and in terms of optical density and reliability, C.I. Pigment Oranges 45, 62, 64, 68, 72 and 77, preferably containing at least one selected from the group consisting of, C.I. It is more preferable to include Pigment Orange 64.

As the purple colorant, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32 , 37, 39, 42, 44, 47, 49, and 50, and in terms of optical density and reliability, C.I. It is preferable to include at least one selected from the group consisting of Pigment Violet 14, 19, 23, 29, 32, 33, 36 and 37, and C.I. It is more preferable to include Pigment Violet 29.

According to one embodiment, the colorant is C.I. By including Pigment Blue 15:3, an orange colorant and a purple colorant, it is possible to provide a black photosensitive resin composition having excellent optical properties without including a black colorant, and thus reliability can be improved.

The colorant may further include a black colorant if necessary, and the black colorant may be appropriately selected from inorganic pigments or organic pigments. Available black colorants include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, lactam black, perylene black, and organic black. The pigment and the organic pigment may be used alone or in combination.

The colorant may be included in an amount of 30 to 55% by weight, preferably 32 to 50% by weight, based on the total weight of solids in the black photosensitive resin composition. When the content of the colorant is included within the above range, optical properties and reliability may be improved.

The blue 15:3 is included in 15 to 45% by weight, preferably 20 to 40% by weight, based on the total weight of the colorant, and the orange colorant and purple colorant are 5 to 50% by weight, preferably 10 to 40% by weight. 45% by weight, and the black colorant may be included in 5 to 35% by weight, preferably 10 to 32% by weight.

(B) alkali soluble resin

The alkali-soluble resin generally makes the non-exposed portion of the black photosensitive resin layer formed using the black photosensitive resin composition alkali-soluble, and may also act as a dispersion medium for the pigment. The alkali-soluble resin may be selected from various polymers used in the applicable technical field, but it may be more effective to include an epoxy group. This is because the alkali-soluble resin containing an epoxy group may affect reliability improvement.

The molecular weight of the alkali-soluble resin is preferably a weight average molecular weight of 3,000 to 20,000, more preferably 5,000 to 15,000.

The acid value of the alkali-soluble resin is preferably 50 to 200 mg·KOH/g based on the solid content in the black photosensitive resin composition. When the acid value is within the above range, there are advantages in that developability against alkali development is excellent, residue generation is suppressed, and adhesion of the pattern is improved.

The alkali-soluble resin may be included in 20 to 39% by weight, preferably 23 to 36% by weight, based on the total weight of solids in the black photosensitive resin composition. When the content of the alkali-soluble resin is included within the above range, it is preferable in that the performance of the colorant can be expressed excellently by increasing the developability, remaining film rate, and dispersibility of the colorant.

(C) photopolymerizable compound

The photopolymerizable compound includes an unsaturated bond and proceeds with a photoreaction with a photopolymerization initiator to form a photosensitive resin layer. The polymerizable compound used in the present invention may include a commonly used (meth)acrylate as a functional group. It may contain an unsaturated group and has photosensitivity, so there is no limit to its use.

Specific examples of the photopolymerizable compound include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and pentaeryth. Litol acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 4- butanediol dimethacrylate, 1, 6- hexanediol dimethacrylate, etc. are mentioned. The photopolymerizable compounds exemplified above may be used alone or in combination of two or more.

The photopolymerizable compound may be included in an amount of 3 to 20% by weight, preferably 6 to 19% by weight, based on the total weight of solids in the black photosensitive resin composition. When the content of the photopolymerizable compound is included within the above range, it is preferable because sensitivity is excellent and pattern characteristics are formed well.

(D) photopolymerization initiator

The photopolymerization initiator serves to initiate a radical reaction of the photosensitive resin composition to cause curing and improve sensitivity. The photopolymerization initiator is a photopolymerization initiator generally used in photosensitive resin compositions, and oxime-based, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, benzoin-based, biimidazole-based compounds and the like may be used.

Examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and the like, including OXE-01 and OXE0-2 commercially available from BASF. more preferable

As an acetophenone compound, for example, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2 -Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1- oligomers of one and the like, preferably 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and the like. In addition, photopolymerization initiators other than the acetophenone type may be used in combination. Photopolymerization initiators other than acetophenone-type include active radical generators, sensitizers, acid generators, and the like that generate active radicals by irradiation with light. Examples of the active radical generating agent include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds. Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone compound include benzophenone, o-benzoylmethyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra( t-butyl peroxycarbonyl) benzophenone, 2,4,6-trimethyl benzophenone, etc. are mentioned. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxy city oxanthone etc. are mentioned. Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl) -6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri Azine, 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-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-methylphenyl)ethenyl]-1,3,5-triazine,2,4-bis(trichloromethyl)-6-[2-(3,4dimethoxyphenyl)ethenyl]-1,3,5 - Triazine etc. are mentioned. Examples of the active radical generating agent include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis(o-chlorophenyl)-4,4', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like can be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate. nate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, and benzoin tosylate, etc. are mentioned. In addition, as an active radical generator, some of the above compounds generate an acid simultaneously with an active radical. For example, a triazine-based photopolymerization initiator is also used as an acid generator.

The photopolymerization initiator may be included in an amount of 0.5 to 4% by weight, preferably 1 to 3.5% by weight, based on the total weight of solids in the black photosensitive resin composition. When the content of the photopolymerization initiator is included within the above range, pattern formation is improved and the black photosensitive resin composition is highly sensitive, so that the strength of the pixel portion formed using this composition and the smoothness on the surface of the pixel portion tend to be good It is desirable because there is

Furthermore, in the present invention, a photopolymerization initiation auxiliary agent may be used. The photopolymerization initiation aid can accelerate the polymerization of the photopolymerizable compound whose polymerization is initiated by the photopolymerization initiator, and one or more compounds selected from the group consisting of carboxylic acid and sulfonic acid compounds may be preferably used.

When the photopolymerization initiator is used in combination with the photopolymerization initiation auxiliary agent, the black photosensitive resin composition containing the photopolymerization initiator becomes more sensitive and productivity is improved when forming a support spacer for maintaining a cell gap using the photopolymerization initiator.

In the case of using the above photopolymerization initiation aid, the amount of the photopolymerization initiator is usually 10 moles or less, preferably 0.01 to 5 moles per mole of the photopolymerization initiator. When it is in the above range, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of a color filter formed using this composition tends to be improved, so it is preferable.

(E) Solvent

The solvent is not particularly limited as long as it has compatibility with the above components and does not react, and various organic solvents used in the field of photosensitive resin compositions may be used.

The solvent is preferably an organic solvent having a boiling point of 100° C. to 200° C. in terms of coating properties and drying properties, and organic solvents having different boiling points may be mixed and 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, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, alkylene glycol alkyl ether acetates such as methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone , acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3- Cyclic esters, such as esters, such as methoxy methyl propionate, and (gamma)-butyrolactone, etc. are mentioned. Among the above solvents, organic solvents having a boiling point of 100°C to 200°C are preferable from the viewpoint of coating properties and drying properties, and more preferably, alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy and esters such as ethyl propionate and 3-methoxymethylpropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxyethylpropionate, 3- methyl methoxypropionate; and the like.

The solvent may be included in an amount of 10 to 90% by weight, preferably 20 to 85% by weight, based on the total weight of the black photosensitive resin composition. When the content of the solvent is included within the above range, it is preferable in that dispersion stability of the black photosensitive resin composition and processability (eg, coatability) in the manufacturing process may be improved.

In other words, the black photosensitive resin composition according to the present invention can produce a black matrix, spacer or black column spacer (black matrix integrated spacer) by wet coating, wherein a roll coater, spin coater, slit and spin A coating device such as a coater, a slit coater (sometimes referred to as a die coater), an inkjet or the like can be used.

additive

The additives may be added to improve coating properties and adhesion, and include silane coupling agents and surfactants.

The silane coupling agent may have a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and combinations thereof.

Specific examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyl triethoxysilane, r-glyc If cidoxy propyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. are mentioned, these can be used individually or in combination of 2 or more types.

The surfactant may improve coating properties of the black photosensitive resin composition.

The surfactant is preferably a fluorine-based surfactant, for example, Megapis F554, F-470, F-471, F-475, F-482 and F-489 (Dinipbon Ink & Chemicals Co., Ltd.) as commercial products. , BM-1000, BM-1100 (BM Chemie Co.), Proride FC-135/FC-170C/FC-430 (Sumitomo 3M Co., Ltd.), and the like. The surfactants exemplified above may be used alone or in combination of two or more.

The additives may be appropriately added and used by those skilled in the art within a range that does not impair the effects of the present invention. For example, the additive may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the black photosensitive resin composition, but is not limited thereto.

The method for producing the black photosensitive resin composition of the present invention is not particularly limited, and follows a known method for producing a black photosensitive resin composition.

For example, after adding the coloring agent to the solvent, the remaining composition and other additives may be added and stirred. At this time, the colorant may be added in the form of a millbase in which a pigment or the like is previously dissolved or dispersed in a solvent or alkali-soluble resin. The additives may be pre-added to the solvent together with the colorant if in solution form.

The black photosensitive resin composition thus prepared may be preferably used in the manufacture of a color filter including a column spacer, a black matrix or a black column spacer, and a display device including the same.

<Color Filter>

A pattern formation method for forming a color filter including a column spacer, a black matrix, or a black column spacer according to a photolithography method may use a method known in the art.

For one embodiment, the pattern forming method,

a) applying a black photosensitive resin composition to a substrate;

b) a prebaking step of drying the solvent;

c) curing the exposed area by applying actinic light to a photomask on the obtained film;

d) performing a developing process of dissolving the unexposed portion using an aqueous alkali solution; and

e) drying and post-baking; may be included.

The substrate may be a glass substrate or a polymer substrate, but is not limited thereto. As the glass substrate, soda lime glass, glass containing barium or strontium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass or quartz can be preferably used. Further, examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone substrates.

At this time, the coating may be performed by a known wet coating method using a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet to obtain a desired thickness. .

Prebaking is performed by heating with an oven, hot plate or the like. At this time, the heating temperature and heating time in the prebake are appropriately selected according to the solvent used, and may be performed for 1 to 30 minutes at a temperature of 80 to 150 ° C, for example.

In addition, the exposure performed after the prebaking is performed by an exposure machine to expose through a photomask, thereby sensitizing only the portion corresponding to the pattern. At this time, as the light to be irradiated, for example, visible light, ultraviolet rays, X-rays, electron beams, and the like can be used.

The development step of dissolving the unexposed portion using an alkaline aqueous solution after exposure is performed for the purpose of removing the photosensitive resin composition of the unremoved portion of the unexposed portion, and a desired pattern is formed by this development. As a developing solution suitable for development using this aqueous alkali solution, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal can be used. In particular, using an aqueous alkali solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate, or lithium carbonate at a temperature of 10 to 50° C., preferably 20 to 40° C., using a developing device or an ultrasonic cleaner. can be done by

The post-baking is performed to increase adhesion between the patterned film and the substrate, and may be performed by heat treatment at, for example, 80 to 250° C. for 10 to 120 minutes. Post-baking, like pre-baking, can be performed using an oven, hot plate, or the like.

At this time, the film thickness of the black matrix is preferably 0.2 μm to 10.0 μm, more preferably 0.5 μm to 7.0 μm, and particularly preferably 1.0 μm to 5.0 μm.

Further, the film thickness of the column spacer and the black column spacer is preferably 0.5 µm to 8 µm, more preferably 0.1 µm to 6 µm, and particularly preferably 0.1 µm to 4 µm.

<Display device>

The display device according to the present invention includes a configuration known in the art, except for the above-described color filter, and specific examples include a liquid crystal display, an OLED, a flexible display, an electroluminescent display, and a plasma display. devices, field emission display devices, and the like, but are not limited thereto.

A color filter including a column spacer, a black matrix, or a black column spacer made of the black photosensitive resin composition of the present invention has an effect of improving the adhesion of the column spacer, the black matrix, or the black column spacer to a substrate, thereby improving the composition of the display device. It can have excellent properties in terms of dynamics and durability.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples may be appropriately modified or changed by those skilled in the art within the scope of the present invention.

Preparation Example: (B) Preparation of Alkali-Soluble Resin

277 g of methoxybutyl acetate was put into a separable flask with an internal volume of 1 liter equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet pipe, and after raising the temperature to 80 ° C, 3,4-epoxytricyclo [5.2. 301 g of a mixture of 1.0,2,6]decan-9-ylacrylate and 3,4-epoxytricyclo[5.2.1.0,2,6]decan-8-ylacrylate [50:50 (molar ratio)]; A copolymer solution [solid content (NV) 35.0 weight %] was obtained. The obtained copolymer had an acid value (dry) of 69.8 mg KOH/g, a weight average molecular weight (Mw) of 12,300, and a degree of dispersion (Mw/Mn) of 2.1.

Preparation of black photosensitive resin composition according to Examples and Comparative Examples

Black photosensitive resin compositions according to Examples and Comparative Examples were prepared with the compositions shown in Table 1 below.

(Unit: g) composition Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 coloring agent O64 2.60 1.60 2.00 1.00 3.20 2.00 1.60 1.80 2.00 2.00 V29 3.00 2.20 2.20 1.60 2.40 1.80 2.20 4.00 2.40 2.00 B15:3 2.80 2.40 2.00 2.00 - - - - - - CB - 1.20 - 2.00 - - - - 1.20 - OBP - - 2.40 1.00 - - 2.40 - - 2.00 B15:6 - - - - 2.80 2.40 2.20 - - - B60 - - - - - 1.20 - 2.00 2.00 2.40 (B) 5.17 6.25 5.21 6.31 5.29 6.35 5.46 5.83 6.26 5.59 (C) 2.66 3.22 2.68 3.25 2.73 3.27 2.81 3.00 3.22 2.88 (D) 0.51 0.62 0.51 0.62 0.52 0.63 0.54 0.57 0.62 0.55 additive 3.26 2.52 3.00 2.22 3.06 2.35 2.79 2.80 2.30 2.58 (E) 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00

(A) Colorant: C.I. Pigment Orange 64 (O64), C.I. Pigment Violet 29 (V29), C.I. Pigment Blue 15:3 (B15:3), Carbon Black (CB), Organic Black (OBP), C.I. Pigment Blue 15:6 (B15:6), C.I. Pigment Blue 60 (B60)

(B) Alkali-soluble resin: see Preparation Example

(C) photopolymerizable compound: dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.)

(D) photopolymerization initiator: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime) (Irgacure OXE-02: Ciba buy)

Additive: F554 (from DIC)

(E) solvent: propylene glycol monomethyl ether acetate (PGMEA)

Test Example: Evaluation of Physical Properties of Black Photosensitive Resin Composition

(1) Substrate fabrication

A 5cmX5cm glass substrate (Corning Co.) was washed with neutral detergent and water and then dried. Each of the black photosensitive resin compositions according to Examples and Comparative Examples was spin-coated on the glass substrate to a final film thickness of 3.0 μm, pre-baked at 80 to 120° C., and dried for 1 to 2 minutes to remove the solvent. Then, a pattern was formed by exposure at an exposure amount of 25 to 35 mJ/cm ² , and an unexposed portion was removed using an aqueous alkali solution. Subsequently, post-baking was performed at 200 to 250° C. for 10 to 30 minutes to prepare a colored substrate.

(2) Reliability evaluation

Based on the manufacturing standards as described above, the substrate is manufactured so that the black photosensitive resin composition is coated on the entire surface without a pattern. It is cut into a size of 3x3 cm, immersed in NMP solvent, and then heated at 100 ° C. for 60 minutes. Thereafter, only the NMP solvent was extracted, and the absorbance was measured using a UV-vis spectrometer to measure the degree of elution into the NMP solvent, and evaluated according to the following evaluation criteria, and is shown in Table 2 below.

<Evaluation Criteria>

- Absorbance within the range of 300 to 800 nm

0.5 or less: ◎ (excellent)

More than 0.5 and less than or equal to 1.0: ○ (good)

More than 1.0 and less than or equal to 1.2: △ (deficient)

Greater than 1.2: X (worsening)

(3) Near-IR transmittance (750nm T%, 950nm T%) evaluation

Based on the manufacturing standards as described above, optical properties are evaluated with a substrate manufactured so that the black photosensitive resin composition is coated on the entire surface without a pattern. Use UV-vis (UV-2550, Shimadzu). Among the wavelength ranges, 700 to 750 nm and 950 nm are near-infrared (Near-IR) regions, and the measured values for each wavelength are confirmed, evaluated according to the following evaluation criteria, and are shown in Table 2 below.

<Evaluation Criteria>

- Transmittance at 750nm

10T% or less: ◎ (Excellent)

More than 10T% to 12T% or less: ○ (good)

More than 12T% and less than or equal to 15T%: △ (short)

Exceeding 15T%: X (Deterioration)

- Transmittance at 950nm

Over 15T%: ◎ (Excellent)

12T% or more to less than 15T%: ○ (good)

10T% or more to less than 12T%: △ (short)

Less than 10T%: X (Worse)

evaluation item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 reliability ◎ ◎ ◎ O △ X X △ X X 750nmT% ◎ ◎ ◎ ◎ △ O ◎ X O ◎ 950nmT% ◎ ◎ ◎ ◎ ◎ O O ◎ O O optical density
(OD/μm) 1.59 1.62 1.65 1.66 1.55 1.58 1.64 1.54 1.61 1.63

Referring to Table 2, the colored substrate according to the embodiment is C.I. It contains Pigment Blue 15:3, and thus it can be confirmed that reliability and light characteristics (transmittance) are excellent.

However, the colored substrate according to the comparative example had C.I. It does not contain Pigment Blue 15:3, instead C.I. It contains Pigment Blue 15:6 and/or 60, and accordingly, it can be confirmed that reliability and optical properties are not good.

Thus, as in the present invention, C.I. In the case of including Pigment Blue 15:3, it can be seen that a black photosensitive resin composition having excellent reliability and optical properties can be provided.

Claims (7)

A black photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent,
With respect to the total weight of solids in the black photosensitive resin composition,
(A) 30 to 55% by weight of a colorant;
(B) 20 to 39% by weight of an alkali-soluble resin;
(C) 3 to 20% by weight of a photopolymerizable compound;
(D) 0.5 to 4% by weight of a photopolymerization initiator; and
Based on the total content of the black photosensitive resin composition, (E) including 10 to 90% by weight of the solvent,
The (A) colorant includes CI Pigment Blue 15:3 and does not contain a black colorant,
When a film is formed from the black photosensitive resin composition, the transmittance at 750 nm is 12T% or less, and the transmittance at 950 nm is 12T% or more.
The method of claim 1,
The (A) colorant further comprises an orange colorant and a purple colorant, characterized in that the black photosensitive resin composition.
The method of claim 2,
The orange colorant is at least one selected from the group consisting of CI Pigment Orange 45, 62, 64, 68, 72 and 77,
The purple colorant is colored photosensitive resin composition, characterized in that it comprises at least one selected from the group consisting of CI pigment violet 14, 19, 23, 29, 32, 33, 36 and 37.
delete delete A color filter comprising a column spacer, a black matrix, or a black column spacer prepared using the black photosensitive resin composition of any one of claims 1 to 3.
A display device comprising the color filter of claim 6.