KR20190094731A - Colored photosensitive resin composition, color pixel and display device produced using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, which has the contact angle of 100 to 160° with respect to water on a surface of a coating film produced after the photocuring and development, has the contact angle of 40 to 70° with respect to propylene glycol methyl ether acetate (PGMEA), and has the contact angle with respect to the water : the contact angle with respect to the propylene glycol methyl ether acetate (PGMEA) = 1 : 0.4 to 0.6, and to a light emitting element and a display device using the same.

Description

Colored photosensitive resin composition and color element and display device manufactured using same {COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR PIXEL AND DISPLAY DEVICE PRODUCED USING THE SAME}

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

Color devices are widely used in various display devices such as imaging devices and liquid crystal display devices (LCDs), and their application ranges are expanding.

Color elements are manufactured by dyeing, printing, pigment dispersion, electrodeposition, and the like, and in recent years, a cost reduction process using an inkjet method has been proposed in accordance with the enlargement of the display material substrate.

For example, in manufacturing a color filter, the partitions constituting the black matrix are previously formed by photolithography, and red, green, and blue inks are sprayed and applied to the openings surrounded by the partitions by an inkjet method to form pixels. Formed. This is the same also in the case of the quantum dot display device that is being studied recently.

In manufacturing an organic EL display element, after forming the partition which comprises a pixel by photolithography, the hole transport material and the light emitting material solution are sprayed and apply | coated by the inkjet method to the opening part enclosed by the partition, and a hole transport layer , A pixel having a light emitting layer or the like is formed. This is the same also in the case of the quantum dot display device that is being studied recently.

The display can be classified into two types. A light source exists at the rear side like a liquid crystal display (LCD) and a color is displayed through a filter or a light conversion layer, and light is generated by applying electricity such as an organic light emitting diode (OLED). Can be distinguished in a way. However, in the case of a quantum dot display device, the light conversion layer may also serve as a light conversion layer and may generate light by applying electrical energy.

In both of the above methods, it is very important to form a partition and to suppress color mixture generated in the device in manufacturing a color device. In the above-mentioned liquid crystal display (LCD), a barrier is formed in black to shield light, and in the case of an organic light emitting diode, a method of suppressing mixed color by depositing a metal is mainly used. Therefore, various methods for preventing color mixing in the manufacture of color devices have been proposed.

In addition, in order to reduce cost and improve productivity, a high sensitivity capable of patterning with a small exposure amount is required for the colored matrix forming material. In addition, due to the high quality of materials used in pixels, the price of materials used to manufacture pixels is soaring, and rather than using spin or slit coating for patterning, the material is used only to the desired part to restrain the use of materials. How to get attention. The most representative method is an inkjet method. The inkjet method uses materials only for desired pixels so that unnecessary waste can be suppressed. The property of bouncing off water, an organic solvent and the like, so-called liquid repellency, is required.

On the other hand, since the ink layer formed in the pixel by the inkjet method is required to have a high film thickness uniformity, the side surface portion or the base portion of the partition wall is required to have wetness property, so-called lyophilic property, with respect to the discharge liquid.

Korean Patent Laid-Open Publication No. 10-2013-0132655 discloses a photosensitive resin composition, a photosensitive element using the same, a method of forming a partition of an image display apparatus, and a method of manufacturing an image display apparatus, but requirements still required for pixel implementation are not satisfied. I can't do it.

Republic of Korea Patent No. 10-1420470 is limited to the contact angle of propylene glycol methyl ether acetate (PGMEA) of more than 20 ° contact angle of water with a compound of a specific chemical structure in the manufacture of partitions having excellent light shielding and liquid repellency Doing. However, the partition wall manufactured through the above invention falls within the range of Comparative Examples 3 to 7 of the present invention and shows a result of inferior inkjet characteristics.

Republic of Korea Patent Publication No. 10-2013-0132655 Republic of Korea Patent No. 10-1420470

An object of this invention is to provide the coloring photosensitive resin composition which is excellent in liquid repellency and can implement the partition which is excellent in the light-shielding property to light other than blue.

Moreover, an object of this invention is to provide the coloring photosensitive resin composition which can form the pixel which a surface defect does not produce.

Moreover, an object of this invention is to provide the color filter and display apparatus manufactured using the coloring photosensitive resin composition mentioned above.

In the present invention, the contact angle with respect to the water of the coating film prepared after the photocuring and development is 100 ° to 160 °, the contact angle with respect to propylene glycol methyl ether acetate (PGMEA) is 40 ° to 70 °, Contact angle for propylene glycol methyl ether acetate (PGMEA) = 1: 0.4 to 0.6 provides a colored photosensitive resin composition characterized in that.

Moreover, this invention provides the color filter manufactured using the coloring photosensitive resin composition mentioned above.

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

In the colored photosensitive resin composition according to the embodiments of the present invention, the contact angle with respect to water and the contact angle with respect to propylene glycol methyl ether acetate (PGMEA) on the surface of the coating film after development respectively exhibit a specific range, and the relationship between each contact angle When having a value within the range of the liquid repellency, it is possible to implement a partition wall excellent in light shielding properties for light other than inkjet blue. Therefore, the coloring photosensitive resin composition by this invention can prevent the ink mixing between the pixels which adjoin each other.

Moreover, the coloring photosensitive resin composition of this invention can form the pixel which a surface defect does not produce.

In addition, the above-mentioned colored photosensitive resin composition can be usefully used for the production of color filters and display devices.

1 to 3 are photographs showing pixel formation measurement results.

According to the present invention, the contact angle with respect to water on the surface of the coating film prepared after the photocuring and development is 100 ° to 160 °, the contact angle with respect to propylene glycol methyl ether acetate (PGMEA) is 40 ° to 70 °, and Contact angle: Contact angle with respect to propylene glycol methyl ether acetate (PGMEA) = 1: 0.4-0.6 It is related with the coloring photosensitive resin composition, the color filter manufactured by the said composition, and a display apparatus.

Hereinafter, the present invention will be described in detail.

<Coloring Photosensitive Resin Composition>

The coloring photosensitive resin composition which concerns on this invention apply | coats a coloring photosensitive resin composition on a board | substrate, photo-cures on the conditions of 40-160 mJ / cm <2> of exposures, and develops in the water (DIW, Deionized Water) of the coating film manufactured by developing. It is preferable that the contact angle with respect to 100 degree-160 degree, and the contact angle with respect to propylene glycol methyl ether acetate (PGMEA) are 40 degree-70 degree.

In the present specification, the contact angle is an angle formed between the solid surface and the tangent to the liquid surface at the point of contact between the solid and the liquid, and is defined as the angle of the side containing the liquid.

If the contact angle with respect to water (DIW, Deionized Water) is less than 100˚ under the above conditions, water may be adsorbed on the partition by the inkjet method, and thus, the inkjet process may not be performed. If it exceeds 160˚, the hydrophobicity may increase. This may cause a problem of ink rolling on the partition wall.

In addition, when the contact angle with respect to propylene glycol methyl ether acetate (PGMEA) is less than 40 degrees, the ink is wetted on the upper part of the partition, making it difficult to manufacture by the inkjet method, and when it exceeds 70 degrees, the flatness of the pattern through the ink jet is too high contact angle. Problems that adversely affect the island may occur.

The colored photosensitive resin composition of the present invention has a contact angle with respect to water: propylene glycol methyl ether acetate (PGMEA) = 1: 0.4 to 0.6 in terms of forming the inkjet method in a uniform pattern and achieving a high yield. good.

The coloring photosensitive resin composition of this invention which has the above-mentioned characteristic can contain (A) binder resin, (B) photopolymerizable compound, (C) photoinitiator, (D) coloring agent, and (E) solvent.

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

(A) binder resin

The colored photosensitive resin composition according to the embodiments of the present invention may include a binder resin that provides adhesion to a substrate to form a coating film, and an alkali-soluble resin may be used as the binder resin.

The alkali-soluble resin usually makes the non-exposed portion of the colored photosensitive resin layer formed using the colored photosensitive resin composition alkali-soluble and also acts as a binder resin and a dispersion medium for the colorant described later.

The alkali-soluble resin may be used without particular limitation as long as it is a polymer soluble in the alkaline developer used in the developing step for manufacturing the color filter. In the present invention, it is preferable to use an alkali-soluble resin including an epoxy group.

The said alkali-soluble resin can mention the monomer containing an epoxy group, the copolymer with the other monomer copolymerizable with the said monomer, etc. are mentioned, for example.

Monomers containing the epoxy groups are specifically, for example, 3,4-epoxytricyclo [5.2.1.0,2,6] decane-9-ylacrylate, 3,4-epoxytricyclo [5.2.1.0,2 , 6] decane-8-ylacrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether and the like.

As another monomer copolymerizable with the monomer containing the said epoxy group, For example, unsaturated carboxylic acid aminoalkyl ester, unsaturated carboxylic acid glycidyl ester, carboxylic acid vinyl ester, unsaturated ether, a vinyl cyanide compound , Unsaturated amides, unsaturated imides, aliphatic conjugated dienes, and macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polysiloxane. The above can be mixed and used.

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

In addition, the acid value of the alkali-soluble resin is 50 to 200mgKOH / g on the basis of solid content, it is excellent in developability for alkali development within the above range, it is possible to suppress the occurrence of residue, and improve the adhesion of the pattern.

The alkali-soluble resin included as the binder resin is included in 30 to 60% by weight relative to the total weight of solids in the colored photosensitive resin composition, it is preferably included in 40 to 50% by weight. When the content of the alkali-soluble resin is within the above range, pattern formation is easy, and resolution and residual film ratio are improved, which is preferable.

Solid content in a coloring photosensitive resin composition in this invention means the sum total of the component which removed the solvent.

(B) photopolymerizable compound

The photopolymerizable compound (B) is a compound capable of polymerization by the action of a photopolymerization initiator, and may include a fluorine compound. In the case of the fluorine-based compound, it has a photopolymerization characteristic together with the photopolymerizable compound. Specific examples for this are 2,2,3,3,3-Pentafluoropropyl acrylate (CAS Number 2993-85-3) to Pentafluorophenyl acrylate (CAS Number 71195-85-2) to 2,2,3,3,3-Pentafluoropropyl acrylate (CAS Number 356-86-5) to 2,2,3,3-Tetrafluoropropyl Methacrylate (CAS Number 45102-52-1), such as a compound having a structure in which fluorine is introduced together with methacrylate to methacrylate It is preferable that it is a polyfunctional compound.

The photopolymerizable compound is contained in 10 to 40% by weight based on the total weight of solids in the colored photosensitive resin composition of the present invention, it is preferably included in 20 to 35% by weight. The said photopolymerizable compound can make the intensity | strength and flatness of a pixel part favorable in the said range.

(C) photopolymerization initiator

The photopolymerization initiator (C) may be used without limitation as long as it can polymerize the photopolymerizable compound. Preferably, the acetophenone compound and the benzoin compound are considered in consideration of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price. It may be one or more compounds selected from the group consisting of benzophenone compounds, triazine compounds, biimidazole compounds, oxime compounds and thioxanthone compounds.

Specifically as the acetophenone-based compound, for example, diethoxyacetophenone, 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 ] Propan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, etc. are mentioned.

Specifically as said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoisobutyl ether, etc. are mentioned, for example.

Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4' -Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloro) Rhomethyl) -6- (4-methoxynaphthyl) -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-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-di Ethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, and 2,4-bis (trichloromethyl) -6- [2- (3,4dimethoxyphenyl) ethenyl] -1 , 3,5-triazine and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2 , 3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl ) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl ), 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, or an imidazole compound in which a phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group Can be mentioned.

More preferably, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4 , 4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole Etc. can be mentioned.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and commercially available products may include BASF's OXE01 and OXE02.

Specific examples of the thioxanthone compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, and 1-chloro-4-propoxythiok. Santon etc. can be mentioned.

The said photoinitiator can be used individually or in mixture of 2 or more types.

In the present invention, the photopolymerization initiator is contained in an amount of 2 to 20% by weight, preferably 5 to 15% by weight, based on the total weight of solids in the colored photosensitive resin composition.

Within this range, the colored photosensitive resin composition may be highly sensitive to improve the strength of the pixel portion formed using the colored photosensitive resin composition and smoothness on the surface of the pixel portion.

In addition, in this invention, a photoinitiator can be used in addition to a photoinitiator.

The photopolymerization initiation aid is a compound used to promote polymerization of the photopolymerizable compound in which polymerization is initiated by the photopolymerization initiator, and examples of the photopolymerization initiation aid include an amine compound or an alkoxy anthracene compound.

Specific examples of the amine compound include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid 2. -Dimethylaminoethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzphenone (collectively, Michler's Ketone), 4,4'-bis (Diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, etc. are mentioned, Among these, 4,4'-bis (diethylamino) benzophenone is preferable.

Specific examples of the alkoxy anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 2-ethyl-9,10- Diethoxy anthracene, and the like.

Moreover, a commercially available thing can be used as a photoinitiator starting adjuvant, As a commercially available photoinitiator adjuvant, brand name "EAB-F" (manufacturer: Hodogaya Chemical Co., Ltd.) etc. are mentioned.

 When using the said photoinitiator, it is preferable to use it normally with more than 0 and 10 mol or less and 0.01-5 mol with respect to 1 mol of photoinitiators. When the photopolymerization initiation aid is used in the range of more than 0 to 10 mol or less, the sensitivity of the colored photosensitive resin composition is higher, and the productivity of the color filter formed using the colored photosensitive resin composition can be improved.

(D) colorant

The coloring photosensitive resin composition of this invention contains at least one of a blue coloring agent and a white coloring agent as a coloring agent.

The colorant may be used in combination of any one or two or more of a pigment, a dye, or a natural dye, and among these, an organic pigment is preferable in that it is excellent in heat resistance and color development. Examples of organic pigments and inorganic pigments include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists), and pigments having the following color index (CI) numbers may be mentioned. It is not necessarily limited to these.

Pigments of color index (C.I.) numbers are for example C.I. Pigment blue 15 (15: 3, 15: 4, 15: 6, etc.), 16, 21, 28, 60, 64, and 76;

C.I. Pigment white 4, 5, 6, 6: 1, and 22;

C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 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, 208, 215, 216, 224, 242, 254, 255, 264 and 279;

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

C.I. Pigment green 7, 10, 15, 25, 36, 47 and 58;

CI Pigment Brown 28;

C.I pigment violet 23, 32 and 29;

C.I Pigment Black 1, 31, 32, and 100 CF from organoblack Basf; Etc. can be mentioned.

These pigments can be used individually or in combination of 2 or more types, respectively.

C.I. exemplified above. Among the pigment pigments, as the blue colorant, C.I. Pigment Blue 15: 6 to 60 is preferred, and the white colorant is C.I. Pigment White 6 is preferred.

The colorant included in the colored photosensitive resin composition of the present invention is included in 5 to 20% by weight, preferably 7 to 15% by weight based on the total weight of solids in the resin composition.

If the colorant is included in the above-described range can be obtained an effect that the optical density is excellent. However, when included in less than 5% by weight is not preferable in terms of optical properties, when included in excess of 20% by weight may be undesirable for reliability and elastic modulus.

 (E) Solvent

As long as the solvent is effective to dissolve the other components included in the colored photosensitive resin composition, the solvent used in the conventional colored photosensitive resin composition can be used without particular limitation, and in particular, ethers, acetates, aromatic hydrocarbons, ketones, Alcohols or esters are preferable.

As said ether, For example, Ethylene glycol monoalkyl ether, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Diethylene glycol dialkyl ether, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, etc. are mentioned.

As the acetates, for example, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 -Methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, di Ethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate and propylene carbonate Can be mentioned.

As said aromatic hydrocarbons, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

As said ketones, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc. are mentioned, for example.

Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 4-hydroxy-4-methyl-2-pentanone, and the like.

As said ester, ethyl 3-ethoxy propionate, methyl 3-methoxy propionate, (gamma) -butyrolactone, etc. are mentioned, for example.

The said solvent can be used individually or in mixture of 2 or more types, respectively.

It is preferable to use the organic solvent whose boiling point is 100 degreeC-200 degreeC from the point of applicability | paintability and dryness, For example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3- Ethyl ethoxy propionate, methyl 3-methoxypropionate, and the like.

The solvent is contained in 50 to 80% by weight, preferably 65 to 75% by weight relative to the total weight of the colored photosensitive resin composition. If the solvent is included in the range of 50 to 80% by weight, the coating property is good when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater) and inkjet Can be done.

(F) additive

The coloring photosensitive resin composition of this invention contains other additive as needed by those skilled in the art in the range which does not impair the objective of this invention other than the above-mentioned components.

The additive may further comprise one or more additives selected from the group consisting of, for example, other polymeric compounds, curing agents, dispersants, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers and anti-agglomerating agents.

Specific examples of the other high molecular compound include curable resins such as epoxy resins and maleimide resins; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The curing agent is used to increase the core hardening and mechanical strength, and specific examples thereof include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin , Glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, cycloaliphatic 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.

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

The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent. Examples of the curing aid compound include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, acid generators, and the like. As said polyhydric carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. Specific examples of the epoxy resin curing agent include commercially available products such as trade names (Adecahadona EH-700, manufactured by Adeka Industrial Co., Ltd.), trade names (manufactured by Rikashitdo HH, Nippon Ewha Co., Ltd.), trade names (MH-700, Shin-Japan Ewha Co., Ltd.) etc. are mentioned. The hardeners illustrated above can be used individually or in mixture of 2 or more types.

The surfactant may be used to further improve the film formability of the photosensitive resin composition, and silicone-based surfactants or fluorine-based surfactants may be preferably used.

The silicone surfactant is, for example, commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA and SH-8400 manufactured by Dow Corning Toray Silicone Co., Ltd., TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF- 4460, TSF-4452, etc. are mentioned. The fluorine-based surfactants are, for example, Megapieces F-470, F-471, F-475, F-482, F-489, and F-554 (Daininib Kagaku Kogyo Co., Ltd.), BM-1000, BM as commercially available products. -1100 (BM Chemie Co., Ltd.), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Corporation), etc. are mentioned. Surfactant illustrated above can be used individually or in combination of 2 types or more, respectively.

The adhesion promoter is an additive used to improve the coating property and adhesion with the substrate, and includes a silane coupling agent including a reactive substituent selected from the group consisting of carboxyl group, methacryloyl group, isocyanate group, epoxy group and combinations thereof. It may include. The silane coupling agent is specifically, for example, trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxy silane, vinyltriacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, r- Glycidoxy propyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

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

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

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The additive may be included in an amount of 0.1 to 10% by weight based on 100% by weight of the colored photosensitive resin composition. When the additive is included in the above range with respect to the colored photosensitive resin composition, there is an advantage in that the desired performance of each additive can be imparted without degrading the performance of the color filter made of the colored photosensitive resin composition.

In addition, the present invention provides a color filter manufactured using the above-described colored photosensitive resin composition and a display device including the same.

The color filter of the present invention comprises a substrate and a color layer formed on the substrate.

The substrate may be a glass plate, a silicon wafer and a plate of a plastic substrate such as polyethersulfone (PES), polyimide (PI), polycarbonate (PC), or the like, and the type thereof is not particularly limited.

The color layer includes a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a colorant, and a solvent, and a coloring photosensitive resin composition comprising an additive as necessary. The colored photosensitive resin composition is coated on a substrate and formed in a predetermined pattern. After that, it may be a layer formed by exposure and development.

Hereinafter, the pattern formation method of the color filter which concerns on this invention is demonstrated in detail.

The pattern forming method of the color filter comprises the steps of applying a colored photosensitive resin composition to a substrate; A prebaking step of drying the solvent; Applying a photomask to the obtained film to irradiate active light to cure the exposed portion; Performing a developing process of dissolving the unexposed portion using an aqueous alkali solution; And performing drying and post-baking.

The substrate is a glass substrate or a polymer plate. Especially as a glass substrate, soda-lime glass, barium or strontium containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, etc. can be used preferably. Moreover, a polycarbonate, an acryl, polyethylene terephthalate, a polyether sulfide, a poly sulfone, etc. are mentioned as a polymer board.

In this case, the coating may be performed by a 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), and an inkjet to obtain a desired thickness.

Prebaking is performed by heating with an oven, a hot plate, etc. At this time, the heating temperature and heating time in a prebaking are suitably selected according to the solvent to be used, and it is performed for 1 to 30 minutes at the temperature of 80 to 150 degreeC, for example.

In addition, exposure performed after a prebaking is performed by an exposure machine, and it exposes only the part corresponding to a pattern by exposing through a photomask. At this time, the light to be irradiated may be visible light, ultraviolet light, X-ray, electron beam, or the like.

It is performed for the purpose of removing the coloring photosensitive resin composition of the part which is not removed of the alkali image development unexposed part after exposure, and a desired pattern is formed by this phenomenon.

As a developer suitable for this alkali image development, the aqueous solution of the carbonate of an alkali metal or alkaline-earth metal, etc. can be used, for example. In particular, using a alkaline aqueous solution containing 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate and lithium carbonate, a developer or an ultrasonic cleaner is used at a temperature of 10 ° C to 50 ° C, preferably 20 ° C to 40 ° C. To perform.

Post-baking is performed to increase the adhesion between the patterned film and the substrate, and is carried out by heat treatment at a temperature of 10 to 120 minutes at 80 ℃ to 230 ℃. Post bake is carried out using an oven, hot plate and the like, like prebaking.

Through the above steps, a pixel or partition wall corresponding to the color of the colorant in the colored photosensitive resin composition can be obtained, and the pattern forming step can be carried out to produce a pattern for performing the inkjet method. The structure of the device may be completed by forming the color ink on the partition wall formed by the inkjet method or by forming the self-luminous ink through the inkjet method, and the construction and the manufacturing method are well known to those skilled in the art. similar.

The display device includes a configuration known to those skilled in the art except that the display device includes a partition wall manufactured using the colored photosensitive resin composition of the present invention.

The partition wall manufactured using the coloring photosensitive resin composition of this invention contains the partition wall which is excellent in liquid repellency and excellent in light-shielding property to light other than blue. As a result, it is possible to prevent color mixing of ink between neighboring pixels, and to improve the reliability of the display device by forming pixels in which surface defects do not occur.

Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the following examples are provided to illustrate the present invention, and the present invention is not limited to the following examples and may be variously modified and changed. The scope of the invention will be defined by the technical spirit of the claims below.

Examples and Comparative Examples

<Manufacture of Substrate>

Dongwoo Phosphorus which is the composition of this invention containing the coloring agent containing at least one of (A) binder resin, (B) photopolymerizable compound, (C) photoinitiator, (D) blue coloring agent, and white coloring agent, and (E) solvent. Chem's SY-O1410 to SY-O1533 solution was coated using a coating machine (Opticoat MS-A150, manufactured by Mikasa) at a rpm capable of exhibiting a certain thickness for each colored photosensitive resin composition, followed by a 90 ° C. hot plate (hot pre-baking for 1 to 10 minutes on the plate) to form a coating film. Thereafter, after the mask for forming a pattern on the coating film, the exposure machine (HB-50110AA, manufactured by Ushio) is irradiated with ultraviolet (UV) exposure according to the amount (mJ / cm 2) shown in Tables 1 to 2 The pattern exposure was performed. After the exposure, the resultant was developed in an alkaline aqueous solution for 80 seconds to dissolve and remove unnecessary portions, and washed with ultrapure water (DIW). The formed portion was thermally cured at a temperature of 220 ° C. for 30 minutes in a convection oven to prepare specimens of Examples 1 to 6 and Comparative Examples 1 to 7. Detailed manufacturing conditions and film thicknesses of Examples 1 to 6 and Comparative Examples 1 to 7 are shown in Tables 1 to 2 below. The SY-O1410 solution used above was C.I. Pigment Blue 15: 6 contains 13% solids and the SY-O1533 solution is C.I. Pigment White 6 pigment is 10% based on solids and C.I. Pigment Blue 15: 6 pigment is included 5% by solids.

Contact angle measurement

The contact angles of the coating films prepared in Examples 1 to 6 and Comparative Examples 1 to 7 were measured using KRUSS's DSA100 product, using respective solvents, and measured in a humidity atmosphere of 40% at a temperature of 25 ° C. Each contact angle was measured every 60 seconds for the contact angle of the solvent and the average value of each contact angle is shown in Tables 1-2.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Photosensitive resin composition SY-O1410 SY-O1410 SY-O1410 SY-O1410 SY-O1533 SY-O1533 Thickness
(Μm) 3.8 3.8 8.0 3.8 4.2 8.5 Exposure amount (mJ / ㎠) 50 80 80 150 80 80 Coating Surface Roughness (Ra, ㎚) 16 26 52 48 26 37 DIW contact angle 115 128 132 148 102 108 PGMEA contact angle 48 55 62 68 44 49 Value of PGMEA Contact Angle / DIW Contact Angle 0.42 0.43 0.47 0.46 0.43 0.45

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Photosensitive resin composition SY-O1410 SY-O1410 SY-O1533 SY-O1410 SY-O1410 SY-O1410 SY-O1410 Thickness
(Μm) 3.8 2.0 4.2 3.8 3.8 3.8 3.8 Exposure amount (mJ / ㎠) 30 300 200 220 280 350 150 Coating Surface Roughness (Ra, ㎚) 12 15 43 15 35 15 25 DIW contact angle 60 81 142 150 170 170 100 PGMEA contact angle 21 18 52 75 68 75 65 Value of PGMEA Contact Angle / DIW Contact Angle 0.35 0.22 0.37 0.5 0.4 0.44 0.65

Pixel formation evaluation test

A pattern substrate was prepared using the colored photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 7 by an inkjet method using quantum dot inks, red inks, and transparent inks prepared as follows. Pixel formation was measured and evaluated. The results are shown in Table 3 below.

Synthesis Example 1 Preparation of Quantum Dot Ink

Quantum dots generally refer to nano-sized particles that emit light at a specific wavelength when injecting light or electrons. The quantum dot particles used in this experiment were designed to see the blue light source, green and red light that were not completely absorbed when the blue light source was inputted with 1: 2 ratio of green and red particles manufactured by Nanoco. . 230mg of green quantum dot particles and 460mg of red quantum dot particles were placed in a 3-neck flask, and BYK's DISPERBYK-111 dispersant was calculated as a solid and 30% of the particles were added.

Quantum dot ink was prepared by adding 8.3 g of SPCY-1L resin, Nippon Showa Polymer Co., Ltd., propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol diacetate (PGDA) at a ratio of 8/2.

Synthesis Example 2 Red Preparation

4.5g of Millbase SC-R324 containing TOYO's Red 254 pigment, 6.8g of SPCY-1L resin from Showa Polymer, Japan, and propylene glycol monomethylether acetate (PGMEA) and propylene glycol diacetate (PGDA) Red ink was prepared by adding 12 g using 7/3 ratio.

Synthesis Example 3) Transparent Ink

3.5g of DPHA (DIPENTAERYTHRITOL PENTA / HEXA ACRYLATE, Nippon Kayaku Co., Ltd.) SPCY-1L resin, 8.3g from Nippon Showa Polymer Co., Ltd. 12 g was used in addition to 3 ratios to prepare a transparent ink.

Pixel formation evaluation

On the substrates prepared in Examples 1 to 6 and Comparative Examples 1 to 7, the color layer was formed by inkjet method using quantum dot inks, red inks, and transparent inks prepared in Synthesis Examples 1) to 3). Were formed to produce color pixels, and pixel formation was measured and evaluated. Pixel evaluation criteria are as follows, and the results are shown in Table 3 below.

<Pixel formation evaluation criteria>

(Double-circle): It judges that the pixel is well formed as shown in FIG.

○: judged to be 90% or more of ink in the substrate

(Triangle | delta): Although the characteristic which fills ink is low like FIG. 2, it is judged that formation of a pixel is possible.

X: It is determined that the formation of pixels is insufficient as shown in FIG.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Quintum Dot Ink ◎ ◎ ◎ ◎ ◎ ◎ △ △ △ X X X △ Red ink ◎ ◎ ◎ ◎ ◎ ◎ X △ X X X X X Transparent ink ○ ◎ ○ ○ ◎ ◎ X X △ X X X X

As can be seen in Table 3, Examples 1 to 6 showed excellent pixel formation when manufacturing color pixels by inkjet method using different inks of quantum dot ink, red ink, and transparent ink. On the other hand, in Comparative Examples 1 to 7, it can be seen that the formation of the pixel is poor.

Specifically, as can be seen in Comparative Examples 3 and 7, even if the DIW contact angle range of 100 to 160 degrees and the PGMEA contact angle range of 40 to 70 degrees are formed, the DIW contact angle: PGMEA contact angle = 1: 0.4 to 0.6 is not satisfied. Otherwise, pixel formation was not easy. In addition, as can be seen in Comparative Examples 4 to 6, even if the ratio of the PGMEA contact angle to the DIW contact angle shows a value of 1: 0.4 to 0.6, the DIW contact angle range is 100 ° to 160 ° and the PGMEA contact angle range is 40 ° to 70 °. If the angle was not satisfied, pixel formation was not easy. From these results, the contact angle for water (DIW), the contact angle for PGMEA, and the ratio of contact angle for water (DIW) and contact angle for PGMEA are correlated, and pixel formation is easily made when certain conditions are satisfied. I could see that.

Claims (10)

After the photocuring and development, the contact angle with respect to water on the surface of the prepared coating film is 100 ˚ to 160 ˚, the contact angle with propylene glycol methyl ether acetate (PGMEA) is 40 ˚ to 70 ˚, and the contact angle with water: propylene Colored photosensitive resin composition whose contact angle with respect to a glycol methyl ether acetate (PGMEA) = 1: 0.4-0.6. The coloring photosensitive resin composition of Claim 1 containing (A) binder resin, (B) photopolymerizable compound, (C) photoinitiator, (D) coloring agent, and (E) solvent.    The coloring photosensitive resin composition of Claim 2 in which a coloring agent contains at least one of a blue coloring agent and a white coloring agent. The method according to claim 3, with respect to the total weight of solids in the colored photosensitive resin composition,
(A) 30 to 60% by weight of the binder resin,
(B) 10 to 40% by weight of the photopolymerizable compound,
(C) 2 to 20% by weight photopolymerization initiator, and
(D) 5 to 20% by weight of a colorant comprising at least one of a blue colorant and a white colorant,
About the total weight of the said coloring photosensitive resin composition,
(E) Colored photosensitive resin composition containing 50-80 weight% of solvents. The coloring photosensitive resin composition of Claim 2 in which the said (B) photopolymerizable compound contains a fluorine-type compound. The coloring photosensitive resin composition of Claim 2 which further contains a fluorine-type additive. The method of claim 3, wherein the blue colorant is C.I. Pigment Blue 15: 6 and the coloring photosensitive resin composition containing 1 or more types chosen from the group which consists of 60. The method of claim 3, wherein the white colorant is C.I. Colored photosensitive resin composition containing pigment white 6. The color element containing the coloring photosensitive resin composition of any one of Claims 1-8. A display device comprising the color element of claim 9.

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