JP2021508087A - Colored photosensitive resin composition, color elements and display devices manufactured using the colored photosensitive resin composition. - Google Patents

Abstract

In the present invention, the contact angle of the coating film surface produced after photocuring and development with water is 100 ° to 160 °, and the contact angle with propylene glycol methyl ether acetate (PGMEA) is 40 ° to 70 °. A colored photosensitive resin composition having a contact angle with water: a contact angle with propylene glycol methyl ether acetate (PGMEA) = 1: 0.4 to 0.6, and a color element using the same. And the display device.

Description

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

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

Color elements are manufactured by a dyeing method, a printing method, a pigment dispersion method, an electrodeposition method, or the like. In recent years, as the size of a display material substrate has increased, a cost reduction process using an inkjet method has been proposed.

For example, in the production of a conventional color filter, a partition wall constituting a black matrix is formed by photolithography, and red, green, and blue inks are sprayed and applied to an opening surrounded by the partition wall by an inkjet method. It was forming pixels. This also applies to the recently studied quantum dot display device.

In the manufacture of an organic EL display element, a partition wall constituting an element (pixel) is formed by photolithography, and then a solution of a hole transporting material and a light emitting material is sprayed and applied to an opening surrounded by the partition wall by an inkjet method. As a result, a pixel having a hole transport layer, a light emitting layer, and the like is formed. This also applies to the recently studied quantum dot display device.

Display can be roughly divided into two types, such as a liquid crystal display (LCD), which has a light source on the rear surface and shows colors by a filter or an optical conversion layer, and an organic light emitting diode (OLED). It can be divided into a method of applying electricity to generate light. However, the quantum dot display element can also serve as an optical conversion layer using light energy, and has a feature that electric energy can be applied to generate light.

In both of the above two methods, when manufacturing a color element, it is very important to form a partition wall and suppress the color mixing generated in the element. The liquid crystal display (LCD) described above uses a method of forming a partition wall in black to block light, and an organic light emitting diode mainly uses a method of suppressing color mixing by a method of depositing metal. .. Therefore, various methods for preventing color mixing have been proposed in the manufacture of color devices.

Further, in order to reduce the cost and improve the productivity, the colored matrix forming material is required to have high sensitivity capable of patterning with a small exposure amount. In addition, the price of materials used for manufacturing pixels is skyrocketing due to the sophistication of materials used for pixels. Therefore, a method of using the material only in a desired portion to minimize the use of the material is attracting attention, rather than performing patterning by performing conventional spin coating or slit coating. The most typical method is an inkjet method. Since the inkjet method uses the material only for the desired pixels, it is possible to suppress unnecessary wasted material. When a color element is manufactured by an inkjet method, the partition wall is required to have a property of repelling water, an organic solvent, etc., which is a discharge liquid of an inkjet, so-called liquid repellency.

On the other hand, since the ink layer formed on the pixels by the inkjet method is required to have high film thickness uniformity, the side surface portion or the base material portion of the partition wall has a property of getting wet with the discharged liquid, that is, so-called liquid friendship. Is required.

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. The requirements for realizing pixels are still not met.

Korean Patent Registration No. 10-142470 describes propylene glycol methyl ether acetate (PGMEA), which has a water contact angle of 90 ° or more, together with a compound having a specific chemical structure, in producing a partition having excellent light-shielding and liquid-repellent properties. ) Is limited to 20 ° or more. However, the partition wall produced by the above invention falls under the range of Comparative Examples 3 to 7 of the present invention, and shows a result inferior in inkjet characteristics.

An object of the present invention is to provide a colored photosensitive resin composition capable of realizing a partition wall having excellent liquid repellency and excellent light shielding property against light other than blue.

Another object of the present invention is to provide a colored photosensitive resin composition capable of forming pixels in which surface defects do not occur.

Furthermore, an object of the present invention is to provide a color element and a display device manufactured by using the above-mentioned colored photosensitive resin composition.

In the present invention, the contact angle of the coating film surface produced after photocuring and development with water is 100 ° to 160 °, and the contact angle with propylene glycol methyl ether acetate (PGMEA) is 40 ° to 70 °. A colored photosensitive resin composition is provided, wherein the contact angle with respect to water: the contact angle with respect to propylene glycol methyl ether acetate (PGMEA) = 1: 0.4 to 0.6.

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

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

In the colored photosensitive resin composition according to the embodiment of the present invention, the contact angle of the coating film surface with water and the contact angle with propylene glycol methyl ether acetate (PGMEA) after development show specific ranges, and each of them shows a specific range. When the relational system of the contact angle has a value within the range of a specific relational system, it is possible to realize a partition having excellent liquid repellency and excellent light shielding property against light other than inkjet blue. Therefore, the colored photosensitive resin composition according to the present invention can prevent color mixing of ink between pixels adjacent to each other.

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

Further, the above-mentioned colored photosensitive resin composition can be usefully used for manufacturing a color element and a display device.

It is a photograph which shows the pixel formation measurement result. It is a photograph which shows the pixel formation measurement result. It is a photograph which shows the pixel formation measurement result.

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

Hereinafter, the present invention will be described in detail.
<Colored photosensitive resin composition>
The colored photosensitive resin composition according to the present invention is produced by applying a colored photosensitive resin composition on a substrate, ^{photocuring under a condition of an exposure amount of 40 to 160 mJ / cm 2} , and then developing the coated surface. The contact angle with water (DIW, Deionized Water) is preferably 100 ° to 160 °, and the contact angle with propylene glycol methyl ether acetate (PGMEA) is preferably 40 ° to 70 °.

In the present specification, the contact angle is the angle formed by the tangent to the surface of the liquid and the surface of the solid at the point where the solid and the liquid come into contact with each other, and is defined as the angle containing the liquid.

Under the above conditions, when the contact angle with water (DIW, Hydrophobic Water) is less than 100 °, there may be a problem that water is adsorbed on the partition wall in the inkjet method and the inkjet method cannot proceed. If it exceeds 160 °, the hydrophobicity increases and the problem of ink rolling on the partition wall may occur.

Further, when the contact angle with respect to propylene glycol methyl ether acetate (PGMEA) is less than 40 °, the ink gets wet on the upper part of the partition wall, which makes it difficult to manufacture by the inkjet method. Too much contact angle can lead to the problem of adversely affecting the flatness of the pattern by inkjet.

The colored photosensitive resin composition of the present invention is formed into a uniform pattern by an inkjet method, and from the viewpoint of obtaining a high yield, the contact angle with water: contact angle with propylene glycol methyl ether acetate (PGMEA) = 1: 0. It is preferably 4 to 0.6.

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

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 the embodiment of the present invention contains a binder resin capable of forming a coating film by imparting adhesion to a base material, and the binder resin is an alkali. Soluble resin can be used.

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

The alkali-soluble resin can be used without particular limitation as long as it is a polymer that can be dissolved in the alkaline developer used in the development step for producing a color filter. However, in the present invention, the alkali-soluble resin contains an epoxy group. It is preferable to use a resin.

Examples of the alkali-soluble resin include a monomer containing an epoxy group and a copolymer of the monomer and another monomer copolymerizable with the monomer.

Specific examples of the monomer containing an epoxy group include 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-ylacrylate and 3,4-epoxytricyclo [5. 2.1.0 ^2,6 ] Decane-8-yl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether and the like.

Examples of other monomers copolymerizable with the monomer containing an epoxy group include unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, and vinyl cyanide. Examples include 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. , Each 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, preferably 5,000 to 15,000 g / mol.

The acid value of the alkali-soluble resin is 50 to 200 mgKOH / g based on the solid content, and when it is within the above range, the developability in alkaline development is excellent, the generation of residue is suppressed, and the pattern adheres. The sex can be improved.

The alkali-soluble resin contained as the 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 the residual film ratio are improved, which is preferable.

In the present invention, the solid content in the colored photosensitive resin composition means the total of the components from which the solvent has been removed.

(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 a photopolymerizable compound. Specific examples for this include 2,2,3,3,3-Pentafluoropropyl acrylicate (CAS Number 2993-85-3) to Pentafluorophenyl compound (CAS Number 71195-85-2) to 2,2,3,3. , 3-Pentafluoropropyl compound (CAS Number 356-86-5) to 2,2,3,3-Tetrafluoropoly Compound (CAS Number 45102-52-1), etc., in which fluorine is introduced together with acrylate to methacrylate. It is preferably a polyfunctional compound containing the compound having the compound.

The photopolymerizable compound is contained in an amount of 10 to 40% by weight, 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 in the above range, the strength and flatness of the pixel portion can be improved.

(C) Photopolymerization Initiator The photopolymerization initiator (C) can be used without limitation as long as it can polymerize a photopolymerizable compound, but preferably, the polymerization characteristics, the initiation efficiency, and the like. One selected from the group consisting of acetophenone compounds, benzoin compounds, benzophenone compounds, triazine compounds, biimidazole compounds, oxime compounds, and thioxanthone compounds in consideration of absorption wavelength, availability, price, etc. It may be the above compound.

Specific examples of the acetphenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2-hydroxy). Ethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) butane-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and 2- (4-methyl) Benzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one and the like can be mentioned.

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

Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert). -Butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

Specific examples of the triazine-based 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-triazine, 2,4-bis (trichloro) Methyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (fran-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 and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbimidazole and 2,2'-bis (2,3-bis). Dichlorophenyl) -4,4', 5,5'-tetraphenyl biimidazole, 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 Examples thereof include'-tetraphenyl-1,2'-biimidazole, or an imidazole compound in which the phenyl group at the 4,4', 5,5'position is replaced with a carboalkoxy group.

More preferably, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', Examples thereof include 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropane-1-one, and commercially available products include OXE01 and OXE02 manufactured by BASF.

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

The photopolymerization initiator 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 it is within the above range, the sensitivity of the colored photosensitive resin composition is increased, and the strength of the pixel portion formed by using the colored photosensitive resin composition and the smoothness on the surface of the pixel portion are good. Can be

Further, in the present invention, a photopolymerization initiator may be used in addition to the photopolymerization initiator.
The photopolymerization initiator is a compound used for accelerating the polymerization of a photopolymerizable compound whose polymerization has been initiated by the photopolymerization initiator, and examples of the photopolymerization initiator include amine compounds or alkoxy. Anthracene-based compounds and the like can be mentioned.

Specific examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid 2. -Dimethylaminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone , And 4,4'-bis (ethylmethylamino) benzophenone, among which 4,4'-bis (diethylamino) benzophenone is preferable.

Specific examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxy. Anthracene and the like.

In addition, commercially available photopolymerization initiators can be used, and commercially available photopolymerization initiators include the trade name "EAB-F" (manufactured by Hodogaya Chemical Co., Ltd.). Be done.

When the photopolymerization initiator is used, it is usually preferably used in an amount of 0.01 to 5 mol, which is more than 0 and 10 mol or less, with respect to 1 mol of the photopolymerization initiator. When the photopolymerization initiator is used in the range of more than 0 and 10 mol or less, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of the color filter formed by using the colored photosensitive resin composition is improved. can do.

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

As the colorant, any one or two or more of pigments, dyes, and natural pigments can be used in combination, and among them, organic pigments are preferable from the viewpoint of excellent heat resistance and color development. Specific examples of the organic pigment and the inorganic pigment include compounds classified as pigments in the Color Index (The Society of Dyers and Colorists Publishing), and the following color indexes (CI) Numbered pigments are mentioned, but not necessarily limited to these.

Examples of the color index (CI) number pigment include C.I. 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); and the like.

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

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, an effect excellent in optical density can be obtained. However, if it is contained in an amount of less than 5% by weight, it is not preferable from the viewpoint of optical characteristics, and if 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, as long as it effectively dissolves other components contained in the colored photosensitive resin composition, the solvent used in the ordinary colored photosensitive resin composition is particularly limited. It can be used without any solvent, and in particular, ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters and the like are preferable.

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 thereof include diethylene glycol dialkyl ethers such as 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 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, diethylene glycol monoacetate, diethylene glycol Examples thereof include 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 the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.

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

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

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

The solvent 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., for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropion. Examples thereof include ethyl acid 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, the coatability is good when applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), and an inkjet. Can be

(F) Additives In addition to the above components, the colored photosensitive resin composition of the present invention contains other additives as necessary by those skilled in the art, as long as the object of the present invention is not impaired.

The additive is, for example, one or more selected from the group consisting of other polymer compounds, curing agents, dispersants, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and antiaggregating agents. Additives may be further included.

Specific examples of the other polymeric compounds include curable resins such as epoxy resins and maleimide resins; thermals such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, and polyurethanes. Examples include plastic resins.

The curing agent is used for deep curing and enhancing mechanical strength, and specific examples thereof include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

Among the curing agents, specific examples of the epoxy compound include bisphenol A-based epoxy resin, hydride bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydride bisphenol F-based epoxy resin, novolak type epoxy resin, and the like. Aromatic epoxy resin, alicyclic epoxy resin, glycidyl ester resin, glycidylamine resin, or an aliphatic or alicyclic resin other than the bromide derivative of such an epoxy resin, the epoxy resin and the bromide derivative thereof. , Or aromatic epoxy compounds, butadiene (co) polymer epoxies, isoprene (co) polymer epoxies, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate and the like.

Among the curing agents, specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

As the curing agent, a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound may be used in combination with the curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. As the polyvalent carboxylic acid anhydride, those commercially available as an epoxy resin curing agent may be used. Specific examples of the epoxy resin curing agent include, as commercially available products, trade name Adeka Hardener EH-700 (manufactured by Adeka Kogyo Co., Ltd.), trade name Ricacid HH (manufactured by New Japan Chemical Co., Ltd.), and trade name MH. -700 (manufactured by New Japan Chemical Co., Ltd.) and the like. The curing agents exemplified above may be used alone or in combination of two or more.

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

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

The adhesion accelerator is an additive used to improve coating property and adhesion to a substrate, and is selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof. A silane coupling agent containing a reactive substituent may be included. Specific examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanoxidetriethoxysilane, and r-glycidoxy. Examples thereof include propyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

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, alkoxybenzophenone and the like.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.
The additive may be contained in an amount of 0.1 to 10% by weight based on 100% by weight of the total amount of the colored photosensitive resin composition. When the additive is contained within the above range with respect to the colored photosensitive resin composition, the performance of the color filter produced from the colored photosensitive resin composition is not deteriorated, and each of the additives There is an advantage that the target performance can be given.

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

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

The color filter of the present invention includes a substrate and a color layer formed on the upper portion of the substrate.

The substrate may be a glass plate, a silicone wafer, a plate of a plastic base material such as polysulfone (PES), polyimide (polyimide, PI), polycarbonate (polycarbonate, PC), etc. It is not limited.

The color layer contains a colored photosensitive resin composition containing a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a colorant, and a solvent, and if necessary, an additive, and the colored photosensitive resin composition. It may be a layer formed by coating an object on a substrate, forming it into a predetermined pattern, and then exposing and developing it.

Hereinafter, the method for forming the pattern of the color filter according to the present invention will be described in more detail.

The method of forming the pattern of the color filter includes a step of applying the colored photosensitive resin composition to the substrate, a prebaking step of drying the solvent, and a photomask applied to the obtained film and irradiated with active light to expose the exposed portion. It includes a step of curing the non-exposed portion, a step of performing a developing step of dissolving a non-exposed portion using an alkaline aqueous solution, and a step of performing drying and post-baking.

As the substrate, a glass substrate or a polymer plate is used. As the glass substrate, soda-lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like can be preferably used. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like.

At this time, 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 (also referred to as a die coater), or an inkjet so that a desired thickness can be obtained. ..

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

Further, the exposure performed after the prebaking is performed by an exposure machine, and by exposing through a photomask, only the portion corresponding to the pattern is exposed. 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 alkaline development after the exposure is carried out for the purpose of removing the colored photosensitive resin composition of the unexposed portion of the unexposed portion, and a desired pattern is formed by this development.

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

Post-baking is performed to improve the adhesion between the patterned film and the substrate, and is performed by heat treatment at 80 ° C. to 230 ° C. for 10 to 120 minutes. Post-baking is performed using an oven, a hot plate, or the like, as in the case of pre-baking.

Through the above steps, pixels or partition walls corresponding to the color of the colorant in the colored photosensitive resin composition are obtained, and by performing such a pattern forming step, a pattern for performing the inkjet method can be produced. Can be done. The structure of the device can be completed by forming a color ink by an inkjet method or a self-luminous ink by an inkjet method on the partition wall manufactured in this way. Its construction and manufacturing method are similar to those known to those skilled in the art in the art of the present invention.

The display device includes a configuration known to ordinary technicians in the technical field of the present invention, except that it includes a partition wall manufactured using the colored photosensitive resin composition of the present invention.

The partition wall produced by using the colored photosensitive resin composition of the present invention includes a partition wall having excellent liquid repellency and light shielding property against light other than blue. As a result, it is possible to prevent color mixing of ink between pixels adjacent to each other, and it is possible to improve the reliability of the display device by forming pixels that do not cause surface defects.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples are for exemplifying the present invention, and the present invention is not limited to the following examples and can be modified and modified in various ways. The scope of the present invention is determined by the technical idea of the appended claims.

Examples and Comparative Examples <Manufacturing of Substrate>
The present invention contains (A) a binder resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a colorant containing at least one of a blue colorant and a white colorant, and (E) a solvent. Toyu Finechem's SY-O1410 or SY-O1533 solution, which is the composition of the above, is made to have a constant thickness for each colored photosensitive resin composition using a coating device (Opticoat MS-A150, manufactured by Mikasa). After coating at a speed capable of polymerizing, prebaking was carried out on a hot plate (hot-plate) at 90 ° C. for 1 minute to 10 minutes to form a coating film. Then, after interposing a mask for forming a pattern on the coating film, an ultraviolet ray ( ^{mJ / cm 2} ) was used in an exposure machine (HB-50110AA, manufactured by Ushio Co., Ltd.) in the amounts (mJ / cm 2) shown in Tables 1 and 2. Pattern exposure was performed while irradiating with UV). After the exposure, unnecessary portions were dissolved and removed by developing with an alkaline aqueous solution for 80 seconds, and then washed with ultrapure water (DIW). The formed portions were subjected to thermosetting at a temperature of 220 ° C. for 30 minutes in a convection oven to prepare test pieces of Examples 1 to 6 and Comparative Examples 1 to 7. Detailed production conditions and film thicknesses of Examples 1 to 6 and Comparative Examples 1 to 7 are shown in Tables 1 and 2 below. The SY-O1410 solution used above is C.I. I. Pigment Blue 15: 6 is contained at 13% on a solid content basis, and the SY-O1533 solution contains C.I. I. Pigment White 6 pigments are 10% on a solids basis, and C.I. I. Pigment Blue 15: 6 pigment is contained in 5% on a solid content basis.

Measurement of contact angle For the contact angle of the coating films produced in Examples 1 to 6 and Comparative Examples 1 to 7, the contact angle of each solvent was measured using a DSA100 product manufactured by KRUSS, and the temperature was 25 ° C. The measurement was performed in a humidity atmosphere of 40%. For each contact angle, the contact angle of the solvent was measured every second for 60 seconds, and the average value of each contact angle is shown in Tables 1 and 2.

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

Synthesis Example 1) Production of Quantum Dot Ink Quantum dots are generally nano-sized particles that emit light of a specific wavelength when light is injected or electrons are injected. The quantum dot particles used in this experiment consisted of green particles and red particles manufactured by Nanoco at a ratio of 1: 2, and when the blue light source was turned on, the blue light source that was not completely absorbed and the green and red light were used. Was designed to be seen at the same time. 230 mg of green quantum dot particles and 460 mg of red quantum dot particles were placed in a three-necked flask (3-Neck flash), and 30% of BYK's DISPERBYK-111 dispersant was added to the particles, calculated in terms of solid content.

Add 8.3 g of SPCY-1L resin from Showa High Polymer Co., Ltd. and 10 g of a solvent prepared by adjusting the ratio of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol diacetate (PGDA) to 8/2, and add quantum dot ink. Manufactured.

Synthesis Example 2) Manufacture of Red Ink 4.5 g of Mill Base SC-R324 product containing Red254 pigment of Toyo Co., Ltd., 6.8 g of SPCY-1L resin of Showa High Polymer Co., Ltd., and propylene glycol monomethyl ether as a solvent. 12 g of acetate (PGMEA) and propylene glycol diacetate (PGDA) were added at a ratio of 7/3 to produce red ink.

Synthesis Example 3) Transparent ink DPHA (DIPENTAERYTHRITOR PENTA / HEXA ACRYLATE, Nippon Kayakusha) 3.5 g, Japan Showa High Polymer Co., Ltd. SPCY-1L resin 8.3 g, and propylene glycol monomethyl ether acetate (PGMEA) as a solvent. And propylene glycol diacetate (PGDA) at a ratio of 7/3 were added in an amount of 12 g to produce a transparent ink.

Pixel formation evaluation Different inks of quantum dot ink, red ink, and transparent ink manufactured in Synthesis Examples 1) to 3) were used for the substrates manufactured in Examples 1 to 6 and Comparative Examples 1 to 7. A color layer was formed by an inkjet method to produce color pixels, and the formation of the pixels was measured and evaluated. The pixel evaluation criteria are as follows, and the results are shown in Table 3 below.

<Pixel formation evaluation criteria>
⊚: Judgment when pixels are well formed as shown in Fig. 1 ○: Judgment at a level where the substrate is filled with 90% or more of ink Δ: As shown in Fig. 2, the characteristics of ink filling are low, but the pixels Judgment when formation is possible X: Judgment when pixel formation is insufficient, as shown in Fig. 3.

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

Specifically, as can be seen from Comparative Examples 3 and 7, even if the DIW contact angle range of 100 ° to 160 ° and the PGMEA contact angle range of 40 ° to 70 ° are formed, the DIW contact angle: PGMEA. When the contact angle = 1: 0.4 to 0.6 was not satisfied, pixel formation was not easy. Further, as can be seen from 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, it is within the range of the DIW contact angle of 100 ° to 160 °. And when the PGMEA contact angle range of 40 ° to 70 ° was not met, pixel formation was not easy. From these results, when the contact angle with water (DIW), the contact angle with PGMEA, and the ratio of the contact angle with water (DIW) and the contact angle with PGMEA have interrelationships and satisfy specific conditions. , It turns out that pixels are easily formed.

In the colored photosensitive resin composition of the present invention, the contact angle of the coating film surface with water and the contact angle with propylene glycol methyl ether acetate (PGMEA) after development show specific ranges, and the contact angles are related to each other. When the system has a value within a specific relational system, it is possible to realize a partition having excellent liquid repellency and excellent light shielding property against light other than inkjet blue. Therefore, the colored photosensitive resin composition according to the present invention can prevent color mixing of ink between pixels adjacent to each other. In addition, the colored photosensitive resin composition of the present invention can form pixels that do not cause surface defects. Further, the above-mentioned colored photosensitive resin composition can be usefully used for manufacturing a color element and a display device.

Claims (10)

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 water. Contact angle with respect to: Propylene glycol methyl ether acetate (PGMEA) contact angle = 1: 0.4 to 0.6, a colored photosensitive resin composition. The colored photosensitive according to claim 1, which comprises (A) a binder resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a colorant, and (E) a solvent. Resin composition. The colored photosensitive resin composition according to claim 2, wherein the colorant (D) contains at least one of a blue colorant and a white colorant. With respect to the total weight of the solid content in the colored photosensitive resin composition
(A) Binder resin 30-60% by weight,
(B) Photopolymerizable compound 10-40% by weight,
(C) 2 to 20% by weight of the photopolymerization initiator, and (D) 5 to 20% by weight of the colorant containing at least one of the blue colorant and the white colorant.
With respect to the total weight of the colored photosensitive resin composition
(E) The colored photosensitive resin composition according to claim 3, which contains 50 to 80% by weight of a solvent. The colored photosensitive resin composition according to claim 2, wherein the photopolymerizable compound (B) contains a fluorine-based compound. The colored photosensitive resin composition according to claim 2, further comprising a fluorine-based additive. The blue colorant is C.I. I. The colored photosensitive resin composition according to claim 3, which comprises one or more selected from the group consisting of Pigment Blue 15: 6 and 60. The white colorant is C.I. I. The colored photosensitive resin composition according to claim 3, which comprises Pigment White 6. A color device containing the colored photosensitive resin composition according to any one of claims 1 to 8. A display device including the color element according to claim 9.

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