JP7541545B2 - Colored photosensitive resin composition, and color element and display device produced using the same - Google Patents

Description

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

Color elements are widely used in various display devices such as image sensors and liquid crystal displays (LCDs), and their range of applications is expanding.

Color elements are manufactured using methods such as dyeing, printing, pigment dispersion, and electrodeposition, and in recent years, with the increase in size of display material substrates, a low-cost process using the inkjet method has been proposed.

For example, in conventional color filter manufacturing, the partition walls that make up the black matrix are formed by photolithography, and red, green, and blue inks are sprayed and applied by the inkjet method into the openings surrounded by the partition walls to form pixels. This is also the case with quantum dot display elements that have been recently researched.

In the manufacture of organic EL display elements, the partitions that make up the elements (pixels) are formed by photolithography, and then solutions of hole transport material and light emitting material are sprayed and applied by the inkjet method into the openings surrounded by the partitions to form pixels having hole transport layers, light emitting layers, etc. This is also the case with quantum dot display elements that have been recently researched.

Displays can be broadly divided into two types: liquid crystal displays (LCDs) have a light source on the back and show color using a filter or light conversion layer, and organic light emitting diodes (OLEDs) generate light by applying electricity. However, quantum dot display elements have the advantage that they can also act as a light conversion layer using light energy, and can also generate light by applying electrical energy.

In both of the above methods, when manufacturing color elements, it is very important to form the partitions and suppress color mixing that occurs in the elements. The above-mentioned liquid crystal display (LCD) uses a method in which the partitions are made of black to block light, while the organic light-emitting diode mainly uses a method of suppressing color mixing by evaporating metal. Therefore, various methods have been proposed to prevent color mixing in the manufacture of color elements.

In order to reduce costs and improve productivity, the color matrix forming material is required to have high sensitivity that allows patterning with a small amount of exposure. In addition, the price of materials used in manufacturing pixels is rising sharply due to the increasing sophistication of materials used in pixels. Therefore, rather than performing patterning by conventional spin coating or slit coating, methods that use materials only in desired areas and minimize the use of materials are attracting attention. The most representative method is the inkjet method. In the inkjet method, materials are used only in desired pixels, so that unnecessary waste of materials can be reduced. When manufacturing color elements by the inkjet method, the partition walls are required to have the property of repelling water and organic solvents, which are the liquids discharged by the inkjet, that is, to have so-called liquid repellency.

On the other hand, the ink layer formed in the pixels by the inkjet method is required to have a high degree of uniformity in thickness, so the side and base portions of the partition walls are required to have the property of being wetted by the ejected liquid, i.e., lyophilicity.

Korean Patent Application Publication No. 10-2013-0132655 discloses a photosensitive resin composition, a photosensitive element using the same, a method for forming a partition wall of an image display device, and a method for manufacturing an image display device, but the requirements for realizing pixels remain unfulfilled.

Korean Patent Registration No. 10-1420470 specifies that in manufacturing a partition wall with excellent light-blocking and liquid-repellent properties, a compound with a specific chemical structure is used, and the contact angle with water is 90° or more, and the contact angle with propylene glycol methyl ether acetate (PGMEA) is 20° or more. However, the partition walls manufactured by the above invention fall within the range of Comparative Examples 3 to 7 of the present invention, and show inferior inkjet characteristics.

The present invention aims to provide a colored photosensitive resin composition that can realize partition walls that are excellent in liquid repellency and light blocking properties against light other than blue light.

Another object of the present invention is to provide a colored photosensitive resin composition that can form pixels that do not cause surface defects.

Furthermore, the present invention aims to provide a color element and a display device manufactured using the above-mentioned colored photosensitive resin composition.

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

The present invention also provides a color element manufactured using the above-mentioned colored photosensitive resin composition.

The present invention also provides a display device including the color element.

The colored photosensitive resin composition according to the embodiment of the present invention can realize a partition wall that has excellent liquid repellency and excellent light blocking properties against light other than inkjet blue light when the contact angle of the coating surface with water and the contact angle with propylene glycol methyl ether acetate (PGMEA) after development each show a specific range and the relationship between the respective contact angles has a value within the specific relationship range. Therefore, the colored photosensitive resin composition according to the present invention can prevent the ink from mixing between adjacent pixels.

In addition, the colored photosensitive resin composition of the present invention can form pixels that do not cause surface defects.

The colored photosensitive resin composition described above can be usefully used in the production of color elements and display devices.

1 is a photograph showing the results of pixel formation measurement. 1 is a photograph showing the results of pixel formation measurement. 1 is a photograph showing the results of pixel formation measurement.

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

The present invention will be described in detail below.
<Colored photosensitive resin composition>
The colored photosensitive resin composition according to the present invention is prepared by applying the colored photosensitive resin composition onto a substrate, photocuring the composition under an exposure condition of 40 to 160 mJ/ ^cm2 , and then developing the composition to produce a coating film having a surface that preferably has a contact angle with water (DIW, deionized water) of 100° to 160° and a contact angle with propylene glycol methyl ether acetate (PGMEA) of 40° to 70°.

In this specification, the contact angle is the angle between the tangent to the liquid surface at the point where the solid and liquid come into contact with each other and the surface of the solid, and is defined as the angle that includes the liquid.

Under the above conditions, if the contact angle with respect to water (DIW, deionized water) is less than 100°, the water may be adsorbed by the partition during the inkjet method, and the inkjet method may not be able to proceed. If it exceeds 160°, the hydrophobicity increases, and the ink may roll on the partition.

In addition, if the contact angle with propylene glycol methyl ether acetate (PGMEA) is less than 40°, the ink will wet the top of the partition wall, making production by the inkjet method difficult, and if it exceeds 70°, the high contact angle can cause problems such as a negative effect on the flatness of the inkjet pattern.

The colored photosensitive resin composition of the present invention is preferably such that the contact angle with water:contact angle with propylene glycol methyl ether acetate (PGMEA)=1:0.4-0.6 in order to form a uniform pattern by the inkjet method and obtain a high yield.

The colored photosensitive resin composition of the present invention having the above-mentioned characteristics may contain (A) a binder resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a colorant, and (E) a solvent.

Hereinafter, each component contained in the colored photosensitive resin composition of the present invention will be described in detail.
(A) Binder Resin The colored photosensitive resin composition according to an embodiment of the present invention contains a binder resin that imparts adhesion to a substrate, thereby enabling the formation of a coating film. As the binder resin, an alkali-soluble resin can be used.

The alkali-soluble resin generally makes the non-exposed area 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 below.

The alkali-soluble resin can be any polymer that is soluble in the alkaline developer used in the development step for manufacturing the color filter, without any particular limitations. In the present invention, however, it is preferable to use an alkali-soluble resin that contains an epoxy group.

Examples of the alkali-soluble resin include monomers containing epoxy groups, and copolymers of the monomers with other monomers that are copolymerizable with the monomers.

Specific examples of the epoxy group-containing monomer include 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-yl acrylate, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether.

Other monomers copolymerizable with the epoxy group-containing monomer include, for example, unsaturated carboxylic acid amino alkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, and macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polysiloxane. These monomers may be used alone or in combination of two or more.

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

In addition, the acid value of the alkali-soluble resin is 50 to 200 mg KOH/g based on the solid content, and when it is within this range, it has excellent developability in alkaline development, suppresses the generation of residues, and improves the adhesion of the pattern.

The alkali-soluble resin contained as a binder resin is contained in an amount of 30 to 60% by weight, preferably 40 to 50% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, a pattern is easily formed, and the resolution and remaining film rate are improved, which is preferable.

In the present invention, the solid content in the colored photosensitive resin composition means the total of the components after removing the solvent.

(B) Photopolymerizable Compound The (B) photopolymerizable compound is a compound that can be polymerized by the action of a photopolymerization initiator, and may contain a fluorine-based compound. The fluorine-based compound is characterized by having photopolymerization properties together with the photopolymerizable compound. Specific examples thereof include polyfunctional compounds including compounds having a structure in which fluorine is introduced together with acrylate or methacrylate, such as 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).

The photopolymerizable compound is contained in an amount of 10 to 40% by weight, and preferably 20 to 35% by weight, based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is contained in the above range, it can improve the strength and flatness of the pixel portion.

(C) Photopolymerization Initiator The photopolymerization initiator (C) can be any compound capable of polymerizing a photopolymerizable compound, but may be one or more compounds selected from the group consisting of acetophenone-based compounds, benzoin-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, oxime-based compounds, and thioxanthone-based compounds, taking into consideration polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like.

Specific examples of the acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one.

Specific examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoisobutyl ether.

Specific examples of the benzophenone-based compounds include benzophenone, 0-benzoylmethylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

Specific examples of the triazine-based compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethene. 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, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine are examples.

Specific examples of the biimidazole compound include 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-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, and imidazole compounds in which the phenyl groups at the 4,4',5,5' positions are substituted with carboalkoxy groups.

More preferred are 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.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, and commercially available products include OXE01 and OXE02 from BASF.

Specific examples of the thioxanthone compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

The photopolymerization initiators may be used alone or in combination of two or more.
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 the solid content in the colored photosensitive resin composition.

When the content is within the above range, the colored photosensitive resin composition is highly sensitive, and the strength of the pixel portion formed using the colored photosensitive resin composition and the smoothness of the surface of the pixel portion can be improved.

In the present invention, a photopolymerization initiator assistant may be used in addition to the photopolymerization initiator.
The photopolymerization initiation assistant is a compound used to promote the polymerization of a photopolymerizable compound whose polymerization has been initiated by a photopolymerization initiator. Examples of the photopolymerization initiation assistant include an amine-based compound and an alkoxyanthracene-based compound.

Specific examples of the amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, with 4,4'-bis(diethylamino)benzophenone being preferred.

Specific examples of the alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene.

In addition, commercially available photopolymerization initiator assistants can be used, and examples of commercially available photopolymerization initiator assistants include "EAB-F" (manufactured by Hodogaya Chemical Co., Ltd.).

When the photopolymerization initiator aid is used, it is usually used in an amount of more than 0 and not more than 10 moles, preferably 0.01 to 5 moles, per mole of the photopolymerization initiator. When the photopolymerization initiator aid is used in the range of more than 0 and not more than 10 moles, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of the color filter formed using the colored photosensitive resin composition can be improved.

(D) Colorant The colored photosensitive resin composition of the present invention contains, as a colorant, at least one of a blue colorant and a white colorant.

The colorant may be any one or a combination of two or more of pigments, dyes, or natural dyes, and among these, organic pigments are preferred because of their excellent heat resistance and color development. Specific examples of organic and inorganic pigments include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists), including pigments with the following Color Index (C.I.) numbers, but are not limited to these.

Color Index (C.I.) number pigments include, 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;
C.I. Pigment Brown 28;
C.I. Pigment Violet 23, 32, and 29;
C.I. Pigment Black 1, 31, 32, and Organic Black 100CF (Basf Corporation);

The pigments may be used alone or in combination of two or more kinds.
Among the C. I. pigment pigments exemplified above, C. I. Pigment Blue 15:6 to 60 is preferred as a blue colorant, and C. I. Pigment White 6 is preferred as a white colorant.

The colorant contained in the colored photosensitive resin composition of the present invention is contained in an amount of 5 to 20% by weight, preferably 7 to 15% by weight, based on the total weight of the solid content in the resin composition.

When the colorant is contained in the above range, it is possible to obtain an excellent effect in terms of optical density. However, when it is contained in an amount of less than 5% by weight, it is not preferable in terms of optical properties, and when it is contained in an amount of more than 20% by weight, it is not preferable in terms of reliability and elastic modulus.

(E) Solvent As the solvent, any solvent used in a typical colored photosensitive resin composition can be used without any particular limitation, so long as it effectively dissolves other components contained in the colored photosensitive resin composition. In particular, ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, and the like are preferred.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
Examples of the diethylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether.

Examples of the acetates include 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 tert-butylene glycol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene 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.

Examples of aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

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

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone.

The above solvents may be used alone or in combination of two or more.
From the viewpoint of coatability and drying property, it is preferable to use an organic solvent having a boiling point of 100° C. to 200° C., and examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.

The solvent is contained in an amount of 50 to 80% by weight, preferably 65 to 75% by weight, based on the total weight of the colored photosensitive resin composition. When the solvent is contained in the range of 50 to 80% by weight, good coatability can be achieved when the composition is applied using a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (also called a die coater), or inkjet.

(F) Additives The colored photosensitive resin composition of the present invention may contain, in addition to the above-mentioned components, other additives according to the needs of those skilled in the art, provided that the object of the present invention is not impaired.

The additives may further include one or more additives selected from the group consisting of other polymer compounds, curing agents, dispersants, surfactants, adhesion promoters, antioxidants, UV absorbers, and anti-aggregation agents.

Specific examples of the other polymer compounds 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 improve deep curing and mechanical strength, and specific examples include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

Specific examples of epoxy compounds among the curing agents include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine 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 epoxidized products, isoprene (co)polymer epoxidized products, glycidyl (meth)acrylate (co)polymers, triglycidyl isocyanurate, etc.

Specific examples of the oxetane compounds among the curing agents include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylate bisoxetane.

The curing agent may be used in combination with a curing auxiliary compound that can cause the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound to undergo ring-opening polymerization. Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators. The polycarboxylic anhydrides may be commercially available as epoxy resin curing agents. Specific examples of the epoxy resin curing agent include commercially available products under the trade name ADEKA HARDNER EH-700 (manufactured by ADEKA Kogyo Co., Ltd.), RIKACID HH (manufactured by New Japan Chemical Co., Ltd.), and MH-700 (manufactured by New Japan Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in a mixture of two or more kinds.

The surfactant can be used to further improve the film-forming properties of the photosensitive resin composition, and silicone-based surfactants or fluorine-based surfactants are preferably used.

Examples of the silicone surfactant include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH-8400 from Dow Corning Toray Silicone Co., Ltd., and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 from GE Toshiba Silicone Co., Ltd. Examples of the fluorine surfactant include commercially available products such as Megafac F-470, F-471, F-475, F-482, F-489, and F-554 (Dainippon Ink and Chemicals Co., Ltd.), BM-1000, BM-1100 (BM Chemie), and Fluorad FC-135/FC-170C/FC-430 (Sumitomo 3M Limited). The surfactants exemplified above may be used alone or in combination of two or more kinds.

The adhesion promoter is an additive used to enhance the coating properties and adhesion to the substrate, and may include a silane coupling agent containing 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 silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, r-glycidoxypropyltrimethoxysilane, 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-chlorobenzotriazole and alkoxybenzophenone.

Specific examples of the anti-aggregating agent include sodium polyacrylate.
The additives may be contained in an amount of 0.1 to 10% by weight, based on the total weight of the colored photosensitive resin composition (100% by weight). When the additives are contained in the colored photosensitive resin composition within the above range, there is an advantage that the performance of a color filter produced from the colored photosensitive resin composition is not deteriorated and the intended performance of each additive can be imparted.

The present invention also provides a color element or color filter manufactured using the above-mentioned colored photosensitive resin composition, and a display device including the same.

The color element of the present invention is not particularly limited as long as it is manufactured by a known manufacturing method for a color element using the above-mentioned colored photosensitive resin composition.

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 silicone wafer, or a plate made of a plastic substrate such as polyethersulfone (PES), polyimide (PI), or polycarbonate (PC), but the type is not particularly limited.

The color layer may be a layer formed by applying a colored photosensitive resin composition containing a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a colorant, and a solvent, and, if necessary, additives, onto a substrate, forming the colored photosensitive resin composition into a predetermined pattern, and then exposing and developing the resulting layer.

The method for forming a color filter pattern according to the present invention is described in more detail below.

The method for forming a color filter pattern includes the steps of applying a colored photosensitive resin composition to a substrate, a pre-baking step for drying the solvent, a step of applying a photomask to the resulting coating and irradiating with active light rays to cure the exposed areas, a developing step for dissolving the non-exposed areas using an alkaline aqueous solution, and a step of drying and post-baking.

As the substrate, a glass substrate or a polymer plate is used. As the glass substrate, particularly preferred are soda-lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. As the polymer plate, polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone are listed.

In this case, the coating may be performed by a wet coating method using a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (also called a die coater), or inkjet to obtain the desired thickness.

Pre-baking is performed by heating in an oven, a hot plate, or the like. The heating temperature and heating time in pre-baking are appropriately selected depending on the solvent used, and are performed, for example, at a temperature of 80°C to 150°C for 1 to 30 minutes.

After pre-baking, the exposure is performed by an exposure machine, and only the parts corresponding to the pattern are exposed by exposing through a photomask. The light to be irradiated can be, for example, visible light, ultraviolet light, X-rays, or electron beams.

After exposure, alkaline development is carried out to remove the colored photosensitive resin composition from the unexposed areas that have not been removed, and the desired pattern is formed by this development.

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

Post-baking is performed to improve adhesion between the patterned film and the substrate by heat treatment at 80°C to 230°C for 10 to 120 minutes. Like pre-baking, post-baking is performed using an oven, hot plate, etc.

Through the above steps, pixels or partitions corresponding to the color of the colorant in the colored photosensitive resin composition are obtained, and by carrying out such a pattern formation step, a pattern for performing the inkjet method can be manufactured. By forming color ink or self-luminous ink on the partitions manufactured in this way by the inkjet method, the structure of the element can be completed. The configuration and manufacturing method are similar to those known to those skilled in the art in the technical field of the present invention.

The display device includes a configuration known to those of ordinary skill in the art of the present invention, except that it is provided with partition walls manufactured using the colored photosensitive resin composition of the present invention.

The partition walls manufactured using the colored photosensitive resin composition of the present invention include partition walls that are excellent in liquid repellency and excellent in light blocking properties against light other than blue light. This makes it possible to prevent ink from mixing between adjacent pixels, and by forming pixels that do not cause surface defects, the reliability of the display device can be improved.

The present invention will be described in more detail below with reference to examples and comparative examples. However, the following examples are for illustrating the present invention, and the present invention is not limited to the following examples, and can be modified and changed in various ways. The scope of the present invention is determined by the technical ideas of the appended claims.

Examples and Comparative Examples <Manufacture of Substrate>
The composition of the present invention, which includes (A) a binder resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a colorant including at least one of a blue colorant and a white colorant, and (E) a solvent, was coated with SY-O1410 or SY-O1533 solution from Dongwoo Finechem Co., Ltd. at an rpm that allows a constant thickness for each colored photosensitive resin composition using a coating machine (Opticoat MS-A150, manufactured by Mikasa Co., Ltd.), and then prebaked for 1 to 10 minutes on a hot plate at 90° C. to form a coating film. Thereafter, a mask for forming a pattern was placed on the coating film, and then pattern exposure was performed while irradiating ultraviolet (UV) rays in an amount (mJ/cm ² ) shown in Tables 1 and 2 using an exposure machine (HB-50110AA, manufactured by Ushio Co., Ltd.). After the exposure, the film was developed in an alkaline aqueous solution for 80 seconds to dissolve and remove unnecessary portions, and then washed with ultrapure water (DIW). The formed portions were thermally cured in a convection oven at a temperature of 220° C. for 30 minutes to prepare test pieces for Examples 1 to 6 and Comparative Examples 1 to 7. Detailed manufacturing conditions and film thicknesses for Examples 1 to 6 and Comparative Examples 1 to 7 are shown in Tables 1 and 2 below. The SY-O1410 solution used above contains 13% C.I. Pigment Blue 15:6 on a solids basis, and the SY-O1533 solution contains 10% C.I. Pigment White 6 pigment on a solids basis and 5% C.I. Pigment Blue 15:6 pigment on a solids basis.

The contact angles of the coatings prepared in Examples 1 to 6 and Comparative Examples 1 to 7 were measured using a DSA100 product manufactured by KRUSS at a temperature of 25° C. and a humidity of 40%. The contact angle of each solvent was measured every second for 60 seconds, and the average values of each contact angle are shown in Tables 1 and 2.

Pixel Formation Evaluation Test Using the quantum dot ink, red ink, and transparent ink prepared as described below, pattern substrates were prepared using the colored photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 7 by an inkjet method, and pixel formation was measured and evaluated. The results are shown in Table 3 below.

Synthesis Example 1) Preparation of Quantum Dot Ink Quantum dots are generally nano-sized particles that emit light of a specific wavelength when light or electrons are injected. The quantum dot particles used in this experiment were designed to be a 1:2 ratio of green and red particles manufactured by Nanoco, and to simultaneously observe the blue light source, which is not completely absorbed, and the green and red lights when a blue light source is introduced. 230 mg of green quantum dot particles and 460 mg of red quantum dot particles were placed in a 3-neck flask, and 30% of BYK's DISPERBYK-111 dispersant was added to the particles, calculated as solid content.

Quantum dot ink was produced by adding 8.3 g of SPCY-1L resin from Showa Polymer Co., Ltd. of Japan and 10 g of a solvent adjusted to an 8/2 ratio of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol diacetate (PGDA).

Synthesis Example 2) Preparation of Red Ink A red ink was prepared using 4.5 g of millbase SC-R324 product containing Red 254 pigment manufactured by Toyo Corporation, 6.8 g of SPCY-1L resin manufactured by Japan Showa Polymer Co., Ltd., and 12 g of a solvent consisting of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol diacetate (PGDA) in a ratio of 7/3.

Synthesis Example 3) Transparent ink A transparent ink was produced by adding 3.5 g of DPHA (DIPENTAERYTHRITOL PENTA/HEXA ACRYLATE, Nippon Kayaku Co., Ltd.), 8.3 g of SPCY-1L resin, and 12 g of a solvent consisting of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol diacetate (PGDA) in a 7/3 ratio.

Pixel Formation Evaluation Color pixels were manufactured by forming color layers by an inkjet method using the quantum dot inks, red ink, and transparent inks manufactured in Synthesis Examples 1) to 3) on the substrates manufactured in Examples 1 to 6 and Comparative Examples 1 to 7, and measuring and evaluating the formation of pixels. The pixel evaluation criteria are as follows, and the results are shown in Table 3 below.

<Pixel formation evaluation criteria>
◎: As shown in Figure 1, pixels are well formed. ○: As shown in Figure 2, the ink is not fully filled on the substrate, but pixels can be formed. △: As shown in Figure 2, the ink is not fully filled on the substrate, but pixels can be formed. X: As shown in Figure 3, pixels are not fully formed.

As can be seen from Table 3, Examples 1 to 6 showed excellent results in pixel formation when color pixels were manufactured by the inkjet method using different inks, namely quantum dot ink, red ink, and transparent ink. In contrast, Comparative Examples 1 to 7 showed poor pixel formation.

Specifically, as can be seen from Comparative Examples 3 and 7, even if the DIW contact angle range was 100° to 160° and the PGMEA contact angle range was 40° to 70°, pixels were not easily formed if the DIW contact angle:PGMEA contact angle = 1:0.4 to 0.6 was not satisfied. Also, as can be seen from Comparative Examples 4 to 6, even if the ratio of the PGMEA contact angle to the DIW contact angle was 1:0.4 to 0.6, pixels were not easily formed if the DIW contact angle range was 100° to 160° and the PGMEA contact angle range was 40° to 70°. From these results, it was found that the contact angle to water (DIW), the contact angle to PGMEA, and the ratio of the contact angle to water (DIW) and the contact angle to PGMEA are interrelated, and pixels are easily formed when certain conditions are met.

The colored photosensitive resin composition of the present invention can realize a partition wall having excellent liquid repellency and excellent light shielding properties against light other than inkjet blue light when the contact angle of the coating surface after development with respect to water and the contact angle with respect to propylene glycol methyl ether acetate (PGMEA) each show a specific range and the relationship between the respective contact angles has a value within a specific relationship. Therefore, the colored photosensitive resin composition according to the present invention can prevent the ink from mixing between adjacent pixels. In addition, the colored photosensitive resin composition of the present invention can form pixels that do not cause surface defects. Furthermore, the above-mentioned colored photosensitive resin composition can be usefully used in the manufacture of color elements and display devices.

Claims (4)

A cured coating film of a colored photosensitive resin composition,
The colored photosensitive resin composition contains, relative to the total weight of the solid content in the colored photosensitive resin composition,
(A) 30 to 60% by weight of an alkali-soluble resin, (B) 10 to 40% by weight of a photopolymerizable compound, (C) 2 to 20% by weight of a photopolymerization initiator, and (D) 5 to 20% by weight of a colorant;
(E) a solvent in an amount of 50 to 80% by weight based on the total weight of the colored photosensitive resin composition;
The photopolymerizable compound (B) contains a fluorine-based compound,
The (C) photopolymerization initiator includes at least one selected from the group consisting of an acetophenone-based compound, a benzoin-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, an oxime-based compound, and a thioxanthone-based compound;
The (D) colorant includes at least one of a blue colorant and a white colorant,
The (E) solvent includes one or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate;
The blue colorant comprises one or more selected from the group consisting of C.I. Pigment Blue 15:6 and 60;
The white colorant comprises C.I. Pigment White 6;
the contact angle of the cured coating film surface to water is 102° to 148°, the contact angle of the cured coating film surface to propylene glycol methyl ether acetate (PGMEA) is 44° to 68°, and the contact angle of the cured coating film surface to water: the contact angle of the cured coating film surface to propylene glycol methyl ether acetate (PGMEA) is 1:0.42 to 0.47;
The contact angle with water and the contact angle with propylene glycol methyl ether acetate (PGMEA) are measured at a temperature of 25° C. and a humidity of 40% . The cured coating according to claim 1 , wherein the colored photosensitive resin composition further comprises a fluorine-based additive. A color element comprising a cured coating according to claim 1 or 2. A display device including the color element according to claim 3.