A colored photo sensitive resin composition, a display partition wall structure prepared using the composition, and a display devide comprising the same

Abstract

The present invention provides a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein a cured film prepared from the colored photosensitive resin composition exhibits constant transmittance characteristics in the wavelength range of the visible light region, and provides a display barrier structure prepared from the colored photosensitive resin composition and a display device including the same.

Description

Technology Field

[0001] The present invention relates to a colored photosensitive resin composition, a display partition structure manufactured using the same, and a display device including the same. Background Technology

[0003] Colored photosensitive resin compositions are essential materials for color filters, liquid crystal display materials, organic light-emitting diodes, displays, etc. For example, in a color filter of a color liquid crystal display, contrast or color rendering effects can be improved by forming a light-blocking layer at the boundary between colored layers such as red, green, and blue.

[0004] Specifically, in pixels composed of red (R), green (G), and blue (B) colors, barriers are formed at the boundaries between the colored layers of each pixel to prevent mixing with other colors or to hide the pattern of the electrodes. Recently, as various image display devices increasingly require high color purity, high brightness, and high contrast, the importance of barriers between pixels is increasing. In particular, in the case of barriers formed adjacent to the colored layers of each pixel, if the optical density (OD) value is excessively high due to their structural characteristics, the transmittance to the light source decreases, which has a problem affecting the color output of the color filter.

[0005] In addition, to efficiently block incident light, a colorant having transmission characteristics in a specific wavelength range is often included in the colored photosensitive resin composition for forming a barrier, depending on the type of light source. However, regarding the photosensitive resin composition for forming the barrier, the colorant used in the conventional colored photosensitive resin composition for forming barriers does not exhibit uniform transmission characteristics in the visible light wavelength range. Furthermore, due to the characteristic that the average particle size of the colorant is larger than that of other colorants, the barrier formed by the conventional colored photosensitive resin composition has a high refractive index, resulting in problems such as high reflectivity for light incident from a light source located below, which leads to reduced visibility of the color filter.

[0006] Korean Registered Patent No. 10-1648607 discloses an ink composition capable of improving contrast ratio, but the aforementioned problems are not sufficiently resolved due to uneven transmittance characteristics to a light source and high reflectivity.

[0007] Therefore, there is a need to develop a colored photosensitive resin composition for forming barriers that has a low specular reflectance to a light source to improve visibility, has an anti-external light reflection effect even without including a polarizer when applied to an organic light-emitting diode, has an optical density (OD) value of less than 1, and exhibits uniform transmission characteristics in the visible light wavelength range. Prior art literature

[0009] Republic of Korea Registered Patent No. 10-1648607 The problem to be solved

[0010] The present invention aims to improve upon the aforementioned conventional technical problems by providing a colored photosensitive resin composition that has a low specular reflectance to a light source, thereby increasing the visibility of the color filter when applied to it, and provides an anti-external light reflection effect when applied to an organic light-emitting diode without including a polarizer.

[0011] In addition, the present invention aims to provide a colored photosensitive resin composition that has an optical density of less than 1 and exhibits uniform transmission characteristics in the visible light wavelength range, so that it does not affect the color development of the color filter even when applied adjacent to the color filter.

[0012] In addition, the present invention aims to provide a display partition structure manufactured using the colored photosensitive resin composition and a display device including the display partition structure.

[0013] However, the problems that the present invention aims to solve are not limited to those mentioned above, and other unmentioned problems will be clearly understood by a person skilled in the art from the description below. means of solving the problem

[0015] The present invention provides a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein a cured film produced from the colored photosensitive resin composition has an optical density (OD) of 1.0 or less and a T value calculated by Formula 1 below of 10 or less when the thickness of the cured film is 1 μm.

[0016] [Equation 1]

[0017]

[0018] (In the above Equation 1, represents the maximum value among the transmittance (%) at λ, λ-100nm, and λ+100nm, and represents the minimum value among the transmittance (%) at λ, λ-100nm, and λ+100nm, and λ is a wavelength between 500nm and 570nm.

[0019] The present invention may have a T value calculated by Equation 1 that is 8 or less when the thickness of the hardened film is 1 μm.

[0020] In the present invention, in the above Equation 1, λ may be a wavelength of 550 nm.

[0021] In the present invention, the color material may include a blue pigment.

[0022] In the present invention, the blue pigment may be one or more selected from CI pigment blue 15:6 and CI pigment blue 60.

[0023] In the present invention, the colored photosensitive resin composition may be characterized as being for forming a barrier.

[0024] In addition, the present invention provides a display partition structure manufactured from the colored photosensitive resin composition.

[0025] In addition, the present invention provides a display device including the display partition structure. Effects of the invention

[0027] A cured film produced by the colored photosensitive resin composition of the present invention has an optical density of less than 1, exhibits constant transmission characteristics in the wavelength range of 380 nm to 780 nm, reduces external light reflection, and exhibits excellent viewing angle characteristics, thereby further improving display visibility. Brief explanation of the drawing

[0029] FIG. 1 is a diagram showing the transmittance spectrum of a patterned cured film prepared using a photosensitive resin composition according to Example 2 and Comparative Examples 3 to 5 of the present invention. Specific details for implementing the invention

[0030] The present invention provides a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein a cured film produced from the colored photosensitive resin composition has an optical density (OD) of 1.0 or less and a T value calculated by Formula 1 below of 10 or less when the thickness of the cured film is 1 μm.

[0031] [Equation 1]

[0032]

[0033] (In the above Equation 1, represents the maximum value among the transmittance (%) at λ, λ-100nm, and λ+100nm, and represents the minimum value among the transmittance (%) at λ, λ-100nm, and λ+100nm, and λ is a wavelength between 500nm and 570nm.

[0034] In the present invention, a forward taper can be understood to mean a case where the taper angle is 90° or less, and a reverse taper can be understood to mean a case where the taper angle is greater than 90°.

[0035] The display device according to the present invention includes a display barrier structure manufactured using the colored photosensitive resin composition, and accordingly, the luminescence characteristics of the display device can be improved.

[0036] In addition, the colored photosensitive resin composition according to the present invention forms a partition structure, and subsequently, when forming a cured film in a thick film, reverse taper formation can be prevented, and thus, the formation of a net taper is easy.

[0037] Among the pure taper bulkhead structures formed in this way, the lower the taper angle, the better the visibility of the color filter. A taper angle of 40° or less is preferable, and 30° or less is even better.

[0038] The present invention will be described in detail below.

[0040] Colored Photosensitive Resin Composition

[0041] The colored photosensitive resin composition according to the present invention is a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the cured film produced from the colored photosensitive resin composition may have an optical density (OD) of 1.0 or less and a T value calculated by the following formula 1 of 10 or less when the thickness of the cured film is 1 μm.

[0042] [Equation 1]

[0043]

[0044] (In the above Equation 1, represents the maximum value among the transmittance (%) at λ, λ-100nm, and λ+100nm, and represents the minimum value among the transmittance (%) at λ, λ-100nm, and λ+100nm, and λ is a wavelength between 500nm and 570nm.

[0045] More preferably, the cured film prepared from the photosensitive resin composition, or the cured film prepared from the colored photosensitive resin composition, may have a T value calculated by Equation 1 of the above formula of 8 or less when the thickness of the cured film is 1 μm. For example, in one embodiment, the cured film has a maximum transmittance among the transmittances at λ, λ-100 nm, and λ+100 nm. Let be denoted as, and the minimum transmittance among the transmittances at the above wavelength When saying, maximum transmittance and minimum transmittance It is characterized by the difference being 10 or less, and accordingly, it can exhibit uniform transmission characteristics in the visible light wavelength range.

[0046] For example, in the above Equation 1, λ may be a wavelength of 550 nm, and in this case, the cured film produced by the above-described colored photosensitive resin composition may have a difference between the maximum transmittance and the minimum transmittance at three wavelengths of 450 nm, 550 nm, and 650 nm of 10 or less. When the above-described cured film satisfies the specific transmittance condition in the specific wavelength range described above, in an organic light-emitting device including a color filter, the light source passing through the barrier is uniformly transmitted to each color filter, thereby providing the effect of improving the light emission characteristics of red (R), green (G), and blue (B) colors.

[0048] (A) Color material

[0049] The colorant included in the colored photosensitive resin composition according to the present invention is not particularly limited as long as it satisfies a transmittance characteristic in which the T value calculated by Equation 1 is 10 or less, and may include two or more colorant combinations. The colored photosensitive resin composition of the present invention may satisfy a transmittance characteristic in which the T value calculated by Equation 1 is 10 or less by including two or more specific colorant combinations, and accordingly may exhibit a constant transmittance characteristic in the visible light wavelength range.

[0050] The colorant included in the colored photosensitive resin composition according to the present invention may include one or more of (a1) blue pigment, (a2) black pigment, (a3) ​​orange pigment and (a4) purple pigment, preferably may include (a1) blue pigment, and more preferably may include (a1) blue pigment and (a2) black pigment.

[0051] In the case of conventional photosensitive resin compositions for forming barriers that include scattering particles such as metal oxides to increase the light efficiency of pixels, transmittance was controlled by adjusting the content of only black pigment. However, when transmittance is lowered using only black pigment, the content of white pigment required to increase reflectance increases significantly, which leads to an increase in the total content of all pigments in the photosensitive resin composition and a decrease in the content of components affecting process stability, such as alkali-soluble resins and photopolymerizable compounds, resulting in a problem where the process characteristics of the photosensitive resin composition deteriorate.

[0052] The photosensitive resin composition according to the present invention includes a specific combination of colorants selected from (a1) a blue pigment, (a2) a black pigment, (a3) ​​an orange pigment, and (a4) a purple pigment in a specific content ratio, thereby improving process stability while exhibiting constant transmittance characteristics in the visible light wavelength range. For example, the photosensitive resin composition according to the present invention may include (a1) a blue pigment in an amount of 10 to 50 weight% based on the solid content of the colorant, and more preferably in an amount of 20 to 40 weight%. When (a2) a black pigment is included in addition to (a1) a blue pigment, the ratio of (a1) a blue pigment to (a2) a black pigment may be 1:3 to 20:1, and more preferably in a ratio of 1:2 to 15:1. When included within the above content range, it is easy to satisfy the T value calculated by Equation 1 being 10 or less, which has the advantage of exhibiting constant transmission characteristics in the visible light wavelength range.

[0054] (a1) Blue pigment

[0055] Specifically, the above blue pigment may be a compound classified as a pigment in the Color Index (published by The Society of Dyers and Colourists), and more specifically, may be a pigment with the following Color Index (CI) numbers, but is not necessarily limited to these. Specifically, blue pigments may be examples such as CI pigment blue 15:3, 15:4, 15:6, 16, 21, 28, and 76, and it is preferable to include one or more selected from the group consisting of CI pigment blue 15:3, pigment blue 15:6, and pigment blue 16.

[0057] (a2) Black pigment

[0058] The above black pigment can be appropriately selected from black organic pigments or black inorganic pigments.

[0059] The above black organic pigment may use one or more selected from the group consisting of lactam black, perylene black, cyanine black, and aniline black, and preferably, perylene black may be used in terms of shielding blue light and improving transmittance in the infrared region.

[0060] The above black inorganic pigment may use one or more selected from the group consisting of carbon black, chromium oxide, iron oxide, and titanium black, and preferably, carbon black may be used for light-blocking properties, surface smoothness, dispersion stability, compatibility with resin, etc.

[0061] The above carbon black is not particularly limited as long as it is a light-blocking pigment, and known carbon black may be used. Specifically, examples of the above carbon black include channel black, furnace black, thermal black, lamp black, etc.

[0062] Examples of available carbon blacks include CHBK-17 from Mikuni Pigment; Systo 5HIISAF-HS, Systo KH, Systo 3HHAF-HS, Systo NH, Systo 3M, Systo 300HAF-LS, Systo 116HMMAF-HS, Systo 116MAF, Systo FMFEF-HS, Systo SOFEF, Systo VGPF, Systo SVHSRF-HS, and Systo SSRF from Tokai Carbon Co., Ltd.; and #200HAF, #10FEF, #50SRF, #55 GF from Nippon Steel & Chemical Co. Diagram Black ∥, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, #3030, #3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B of Mitsubishi Chemical Corporation; Daegu Corporation's PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101;RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820 from Columbia Carbon Co., Ltd. RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, Examples include the RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170.

[0063] In addition, the carbon black mentioned above may be resin-coated carbon black. Since the resin-coated carbon black has lower conductivity compared to carbon black not coated with resin, it can provide excellent electrical insulation when forming a black matrix or black column spacer.

[0064] In addition, depending on the purpose, black organic pigments and black inorganic pigments can be used alone or in a mixture of two or more types.

[0066] (a3) Orange pigment

[0067] As for the above-mentioned orange pigment, pigments known in the field may be used if they satisfy the conditions described above. Specifically, orange pigments such as CI pigment orange 13, 15, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71, which are classified as pigments in the Color Index (published by The Society of Dyers and Colourists), may be used.

[0069] (a4) Purple pigment

[0070] Specifically, the above-mentioned purple pigment may be compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists), and more specifically, pigments with the following Color Index (CI) numbers may be used, but are not necessarily limited to these. Specifically, for example, violet pigments such as CI pigments Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, and 38 may be used as purple pigments.

[0072] The above (a1) blue pigment, (a2) black pigment, (a3) ​​orange pigment, and (a4) purple pigment may be included in an amount of 1 to 30 weight%, preferably 10 to 20 weight%, based on the solid content of the colored photosensitive resin composition. If included in an amount less than the above, the transmittance for light in the wavelength range of approximately 450 nm increases, which may cause color mixing between pixels; if included in an amount exceeding the above, the reflectance for light in the wavelength range (550 to 650 nm) generated from red pixels and green pixels decreases, which may cause a problem of reduced luminous efficiency of the display. When the sum of the above (a1) blue pigment, (a2) black pigment, (a3) ​​orange pigment, and (a4) purple pigment is within the above range, the content of each pigment can be freely adjusted within the range satisfying Equation 1.

[0074] (a5) Pigment dispersant

[0075] The pigment dispersant is added to deagglomerate pigments and maintain stability, and any commonly used in the field may be used without limitation. Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants, and each of these may be used individually or in combination of two or more types.

[0076] In addition, the pigment dispersant preferably comprises an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) comprising butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). It is preferable to use an acrylate-based dispersant manufactured by a living control method, and commercially available products include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and each of the acrylate-based dispersants may be used individually or in a mixture of two or more types.

[0077] The pigment dispersant mentioned above may use other resin-type pigment dispersants in addition to acrylate-based dispersants. The other resin-type pigment dispersants mentioned above include known resin-type pigment dispersants, particularly polyurethanes, polycarboxylic acid esters represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partially)amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modification products, or oily dispersants such as amides or salts formed by the reaction of a polyester having a free carboxyl group with a poly(lower alkyleneimine); Examples include water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; polyesters; modified polyacrylates; adducts of ethylene oxide / propylene oxide; and phosphate esters.

[0078] As for the commercially available pigment dispersants of the other resin type mentioned above, cationic resin dispersants include, for example, BYK Chem’s trade names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF product names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Lubrizol product names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemical product names: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Examples include Ajinomoto's product names: Ajisper PB-821, Ajisper PB-822, Ajisper PB-823; Kyoei Chemical's product names: Florene DOPA-17HF, Florene DOPA-15BHF, Florene DOPA-33, Florene DOPA-44, etc.

[0079] In addition to the above-mentioned acrylate-based dispersant, other resin-type pigment dispersants may be used individually or in a mixture of two or more types, and may also be used in combination with the acrylate-based dispersant.

[0080] The pigment dispersant may be included in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the solid content of the colorant. It is preferable that the content of the pigment dispersant be within the above range so that dispersed pigments with uniform particle sizes can be obtained. If the content of the dispersant exceeds 50 parts by weight, the viscosity may increase, and if it is less than 1 part by weight, it may be difficult to micronize the pigment or cause problems such as gelation after dispersion.

[0082] (B) Alkali-soluble resin

[0083] The alkali-soluble resin of the present invention is a component that imparts solubility to the alkaline developer used in the developing process, and acts as a dispersion medium for the pigment.

[0084] The above alkali-soluble resin may be used without limitation as long as it is soluble in an alkali developer, and preferably may include a cardo-based alkali-soluble resin, an acrylic-based alkali-soluble resin, or a mixture thereof.

[0085] The above-mentioned cardo-based alkali-soluble resin has reactivity and alkali solubility in response to the action of light or heat, and the cardo-based alkali-soluble resin contained in the colored photosensitive resin composition of the present invention performs the function of a binding resin for a colorant containing a white pigment, and is not limited to any resin that is soluble in an alkaline developer.

[0086] The cardo-based alkali-soluble resin of the present invention may comprise one or more of the compounds represented by Formula 1-1 and Formula 1-2.

[0087] [Chemical Formula 1-1]

[0088]

[0089] [Chemical Formula 1-2]

[0090]

[0091] In the above Formula 1-1 or Formula 1-2, R1, R2, R3, and R4 are each independently an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or is,

[0092] X is a hydrogen atom; an alkyl group having 1 to 5 carbon atoms; or a hydroxyl group, and

[0093] R5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0094] In the present invention, the compound represented by Chemical Formula 1-1 is synthesized into the compound represented by Chemical Formula 2-1 below, and the compound represented by Chemical Formula 1-2 can be synthesized using the compound represented by Chemical Formula 2-2.

[0095] [Chemical Formula 2-1]

[0096]

[0097] [Chemical Formula 2-2]

[0098]

[0099] The above acrylic alkali-soluble resin is preferably prepared by copolymerizing an ethylene unsaturated monomer having a carboxyl group.

[0100] Specific examples of ethylenically unsaturated monomers having carboxyl groups include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of the above dicarboxylic acids; and mono(meth)acrylates of polymers having carboxyl and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, and acrylic acid and methacrylic acid are preferred.

[0102] In addition, the alkali-soluble resin can be prepared by polymerizing an unsaturated monomer copolymerizable with the ethylenically unsaturated monomer having the carboxyl group.

[0103] Specific examples of the above copolymerizable unsaturated polymer monomers include glycidyl methacrylate, which is an unsaturated monomer having a glycidyl group; and ethylenically unsaturated monomers having a hydroxyl group, such as hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, N-hydroxyethyl acrylamide, etc., which are hydroxyethyl (meth)acrylates. Aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether; N-substituted maleimide compounds such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, etc.; Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] Alicyclic (meth)acrylates such as decane-8-yl (meth)acrylate, 2-dicyclofentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate; unsaturated oxetane compounds such as 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane; etc., but are not limited thereto.

[0104] Each of the above copolymerizable unsaturated monomers can be used individually or in combination of two or more types.

[0106] It is preferable that the acid value of the alkali-soluble resin is 30 to 200 mgKOH / g. If the acid value of the alkali-soluble resin is less than 30 mgKOH / g, it is difficult to secure a sufficient development speed for the colored photosensitive resin composition, and if it exceeds 200 mgKOH / g, adhesion to the substrate decreases, making it easy for short circuits to occur in the pattern, and compatibility with the colorant becomes a problem, causing the colorant within the photosensitive resin composition to precipitate or the storage stability of the photosensitive resin composition to decrease, making it easy for viscosity to increase.

[0107] The above 'acid value' is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1g of acrylic polymer, and can typically be obtained by titrating using an aqueous potassium hydroxide solution.

[0108] In addition, a cardo-based resin or an acrylic alkali-soluble resin having a polystyrene equivalent weight-average molecular weight (hereinafter simply referred to as "weight-average molecular weight") measured by gel permeation chromatography (GPC; using tetrahydrofuran as the elution solvent) of 2,000 to 20,000, preferably 3,000 to 10,000, is preferred. Within the above molecular weight range, film loss during the development process can be suppressed and pattern stability can be improved.

[0110] The alkali-soluble resin may be included in an amount of 5 to 85 weight%, preferably 5 to 60 weight%, based on the total weight of the colored photosensitive resin composition according to the present invention. When the alkali-soluble resin is included within the above range, it is desirable because the solubility in the developer is sufficient to facilitate the formation of a cured film, and the reduction of the film in the pixel portion of the exposed area is prevented during development, thereby improving the omission of the unexposed area.

[0112] (C) Photopolymerizable compound

[0113] The above photopolymerizable compound is a compound capable of polymerizing by light and heat, and any photopolymerizable compound known in the art that can be polymerized by light and heat may be selected and used without special limitations, and specifically, monofunctional monomers, difunctional monomers, other polyfunctional monomers, etc. may be used.

[0114] The types of the monofunctional monomer, the difunctional monomer, and the polyfunctional monomer are not particularly limited, and for example, as the polyfunctional monomer, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. may be used.

[0115] The content of the above photopolymerizable compound may be 5 to 50 weight%, preferably 10 to 40 weight%, based on the total weight of the solids in the colored photosensitive resin composition. When the above photopolymerizable compound is included within the above range, it is desirable in terms of the intensity or smoothness of the pixel portion.

[0117] (D) Photopolymerization initiator

[0118] The above photopolymerization initiator may be selected from photopolymerization initiators known in the art without any particular limitations. For example, acetophenone-based, benzophenone-based, triazine-based, thioxantone-based, oxime-based, benzoin-based, non-imidazole-based compounds, etc., may be used.

[0119] For example, o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one can be used as the above-mentioned oxime-based compound, and OXE-01 and OXE-02 from Ciba are representative commercial products.

[0120] The above photopolymerization initiator can be used alone or in a mixture of two or more types.

[0121] The content of the above photopolymerization initiator may be included in an amount of 0.01 to 10 weight%, preferably 0.01 to 5 weight%, based on the total weight of the solids in the photosensitive resin composition. It is desirable that the above photopolymerization initiator be included within the above range, as the photopolymerization reaction rate is appropriate, thereby preventing an increase in the overall process time and preventing a deterioration in the physical properties of the final cured film due to the photoreaction.

[0122] The colored photosensitive resin composition according to the present invention may further include a photopolymerization initiation aid in addition to the photopolymerization initiator. It is preferable to use a photopolymerization initiation aid together with the photopolymerization initiator, as this makes the colored photosensitive resin composition more sensitive and improves productivity.

[0123] The above photopolymerization initiation aid is a compound used to promote the polymerization of a photopolymerizable compound whose polymerization has been initiated by the above photopolymerization initiator, and one or more compounds selected from the group consisting of amines and carboxylic acid compounds may preferably be used.

[0124] The above photopolymerization initiation aid may be included in an amount of typically more than 0 moles and less than or equal to 10 moles, preferably 0.01 moles and 5 moles, per 1 mole of the above photopolymerization initiator. When the above photopolymerization initiation aid is included within the above range, the photopolymerization efficiency can be improved, and an effect of improving productivity can be expected.

[0126] (E) Solvent

[0127] The above solvent is not particularly limited and various organic solvents known in the field of colored photosensitive resin compositions may be used.

[0128] The above solvent may preferably be an organic solvent having a boiling point of 100°C to 200°C in terms of coating properties and drying properties, more preferably alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate or methyl 3-methoxypropionate may be used, and even more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate may be used. Each of the above solvents may be used individually or in a mixture of two or more types.

[0129] The content of the above solvent may be 60 to 90 weight%, preferably 70 to 85 weight%, based on the total weight of the colored photosensitive resin composition. It is desirable that the solvent be included within the above content range, as this provides the effect of improving applicability when applied using an application device such as a roll coater, spin coater, slit-and-spin coater, slit coater (sometimes also called a die coater), or inkjet.

[0131] heat curing agent

[0132] The colored photosensitive resin composition according to the present invention may further include a thermal curing agent as needed, and when the thermal curing agent is further included, when a cured product is formed using the colored photosensitive resin composition, the deep curing of the cured product or the mechanical strength of the cured product can be improved.

[0133] The above-mentioned thermosetting agent may be selected from the group consisting of, for example, monofunctional alicyclic epoxy resins, silane-modified epoxy resins, and novolak-type epoxy resins.

[0134] The content of the above-mentioned heat-curing agent may be included in an amount of 0.05 to 10 weight%, preferably 0.1 to 10 weight%, based on the total weight of the solids in the photosensitive resin composition. When the heat-curing agent is included within the above range, there is an advantage that chemical resistance is improved, and heat resistance and development speed can be improved.

[0136] additives

[0137] The colored photosensitive resin composition according to the present invention may further include additives as needed, and the types of said additives may be determined according to the user's needs and are not specifically limited in the present invention, but examples include fillers, other polymer compounds, surfactants, adhesion promoters, antioxidants, anti-aggregation agents, etc.

[0138] The above antioxidant may include, for example, one or more selected from the group consisting of phosphorus-based antioxidants, sulfur-based antioxidants, and phenolic-based antioxidants, and in this case, it can suppress color change phenomena that may occur at high temperatures during the process or yellowing that may be caused by a light source after the display is manufactured. The above antioxidant may include one or more selected from the group consisting of phenolic compounds, phosphorus-based compounds, and sulfur-based compounds, and these may be used as a combination of phenolic-phosphorus-based compounds, phenolic-sulfur-based compounds, phosphorus-sulfur-based compounds, or phenolic-phosphorus-sulfur-based compounds.

[0139] The content of the antioxidant may be 0.1 to 30 weight%, preferably 0.5 to 20 weight%, based on the total weight of the solids in the colored photosensitive resin composition. When the antioxidant is included within the above range, it is desirable in terms of solving the problem of reduced luminous intensity, and there is an advantage in that it can be expected to prevent aging caused by heat during post-baking in the process of forming a cured product and preserve the color.

[0140] For additives among the above additives whose content is not exemplified, those skilled in the art may appropriately add and use them within a range that does not impede the effects of the present invention. For example, the above additive may be used in an amount of 0.05 to 10 weight%, preferably 0.1 to 10 weight%, and more preferably 0.1 to 5 weight%, based on the total weight of the photosensitive resin composition, but is not limited thereto.

[0141] The photosensitive resin composition of the present invention can be manufactured by conventional methods known in the art, and is not specifically limited in the present invention, but, for example, can be manufactured by the following method.

[0142] The colorant is mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle size of the colorant is approximately 200 nm or less. At this time, a pigment dispersant is used as needed, and in some cases, part or all of the alkali-soluble resin is incorporated. After adding the remainder of the alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and additional additives as needed to the obtained dispersion, additional solvent is added as needed to reach a predetermined concentration to obtain the desired photosensitive resin composition.

[0144] The colored photosensitive resin composition of the present invention, comprising the (A) colorant, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photopolymerization initiator, and (E) solvent described above, has an optical density (OD) of 1.0 or less and satisfies a T value calculated by Equation 1 of the above of 10 or less when the thickness of the cured film is manufactured to 1 μm, thereby exhibiting uniform transmission characteristics in the wavelength range of the visible light region. The cured film manufactured with the colored photosensitive resin composition of the present invention is included as a component of a display barrier structure and plays a role in helping to ensure that a light source passing through the barrier structure is uniformly transmitted to each color filter.

[0146] < Display bulkhead structure and display device >

[0147] In addition, the present invention provides a display partition structure comprising a cured film made of a colored photosensitive resin composition according to the present invention, and a display device comprising the same.

[0148] Since a display including a barrier structure forms an image by driving each pixel, a thin-film transistor is formed to drive each pixel, an insulating film is additionally formed due to the shape of the transistor, and subsequently, a barrier structure is formed to distinguish between pixels. When the barrier structure is formed using the photosensitive resin composition of the present invention, color mixing of pixels in the display is prevented and it is advantageous for forming a micro-cured film, thereby having the advantage of enabling the realization of high-quality images.

[0149] Display devices may include liquid crystal displays, organic light-emitting diodes, flexible displays, etc., but are not limited thereto, and all display devices known in this field that are applicable can be exemplified. In particular, the present invention can be applied to organic light-emitting diodes, and among them, to organic light-emitting diodes that do not include a polarizer.

[0150] A partition structure can be manufactured by applying the photosensitive resin composition of the present invention described above onto a substrate, and forming a cured film by photocuring and developing.

[0151] First, a smooth cured film is obtained by applying the photosensitive resin composition of the present invention onto a substrate and then heating and drying to remove volatile components such as solvents.

[0152] The coating method may be carried out by, for example, spin coating, flexible coating, roll coating, slit-and-spin coating, or slit coating. After coating, heating is performed after heat drying (pre-baking) or vacuum drying to volatilize volatile components such as solvents. Here, the heating temperature is typically 70 to 150°C, preferably 80 to 130°C. Ultraviolet light is irradiated onto the cured film obtained in this way through a mask to form a cured film of a desired pattern. At this time, it is preferable to use devices such as a mask aligner or a stepper so that parallel light rays are irradiated uniformly across the entire exposure area and accurate positional alignment between the mask and the substrate is achieved. When ultraviolet light is irradiated, curing occurs in the irradiated area.

[0153] The above ultraviolet rays may include g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm), etc. The amount of ultraviolet irradiation can be appropriately selected as needed, and the present invention does not limit this. By contacting the cured film, after photocuring is completed, with a developer to dissolve the unexposed portion and develop it, a cured film shape with a desired pattern can be formed.

[0154] The cured film shape obtained in this way can be hardened through a post-curing process, and the heating temperature is typically 80°C to 250°C, preferably 100°C to 230°C. The heating time is typically 5 to 50 minutes, preferably 15 to 30 minutes. The thickness of the cured film after heat drying is typically about 0.5 to 3 μm.

[0156] The present invention will be described in more detail below based on embodiments, but the embodiments of the present invention disclosed below are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined in the claims, and furthermore, it includes all modifications within the meaning and scope equivalent to the claims. In addition, "%" and "parts" indicating content in the following examples and comparative examples are based on mass unless specifically stated otherwise.

[0158] Synthesis Example 1: Preparation of Color Dispersion Resin

[0159] 270 g of methoxybutyl acetate was added to a 1-liter volume separating flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, and after raising the temperature to 80°C, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-9-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 2,6 A mixed solution comprising 294 g of a mixture of decane-8-yl acrylate [50:50 (molar ratio)], 14 g of dicyclopentenyl acrylate, 42 g of acrylic acid, and 30 g of azobisdimethylvaleronitrile dissolved in 350 g of methoxybutyl acetate was added dropwise over 5 hours, followed by aging for 3 hours to obtain a copolymer solution [solid content (NV) 35.8 wt%]. The acid value (dry) of the obtained copolymer was 90.5 KOH mg / g, the weight-average molecular weight (Mw) was 9500, and the degree of dispersion (Mw / Mn) was 1.8.

[0161] Examples and Comparative Examples: Preparation of Colored Photosensitive Resin Compositions

[0162] Colored photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 6 were prepared according to Table 1 below. Each component was added so that the proportion of the solid content of the composition was the mixing ratio of Table 1, and PGMEA was added as a solvent so that the content of the total solid content was 20 mass%, and the mixture was stirred and dissolved to prepare a colored photosensitive resin composition.

[0163] Unit: Weight % Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Coloring material OBP 13 12 3 10 CB 7 1 8 6 5 5 B15:6 7 10 12 9 20 B60 5 V29 7 5 O64 3 7 10 Perylene Black 2 8 Dispersant 5 3 5 5 2.5 3 1.5 3 3.75 3.25 8.75 dispersion resin 5 3 5 5 2.5 3 1.5 3 3.75 3.25 8.75 Alkali-soluble resin CX-65-C 44.9 53.6 44.9 44.9 55.8 53.6 60.1 53.6 50.4 52.5 28.7 photopolymerizable compounds A-DPH-12E 21.4 24.3 21.4 21.4 25.0 24.3 26.4 24.3 23.2 23.9 16.0 Photopolymerization initiator PBG-327 3.6 4.0 3.6 3.6 4.1 4.0 4.4 4.0 3.8 4.0 2.7 additives F554 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

[0164] - Coloring material

[0165] OBP: Irgaphor Black S 0100 CF (Basf)

[0166] CB : #200HAF (Nippon Steel & Chemical)

[0167] B15:6 : CI Pigment Blue 15:6

[0168] B60 : CI Pigment Blue 60

[0169] V29 : CI Pigment Violet 29

[0170] O64 : CI Pigment Orange 64

[0171] Perylene Black: CI Pigment Black 32

[0172] Dispersant: DISPERBYK-2000

[0173] Dispersion resin: Colorant dispersion resin of Synthetic Example 1

[0174] Alkali-soluble resin (binder resin): CX-65-C (SHOWA DENKO KK Functional Polymers Department.)

[0175] Photopolymerizable monomer: Ethoxylate dipentaerythritol pentaacrylate (A-DPH-12E, Shinnakamura Chemical)

[0176] Photopolymerization initiator: PBG-327 (Tronley)

[0177] Additive: F554 (DIC)

[0178] Solvent: PGMEA

[0180] Experimental example

[0181] (1) Measurement of Transmittance (Transmittance%)

[0182] A 5cm x 5cm glass substrate (Corning) was washed with a neutral detergent and water, and then dried. Each of the colored photosensitive resin compositions prepared in the above examples and comparative examples was spin-coated onto the glass substrate to achieve a final film thickness of 1.0 μm, and the mixture was pre-fired at 100°C and dried for 2 minutes to remove the solvent. Then, an exposure dose of 100 mJ / cm² 2 A hardened film was produced by full exposure to light, developing for 150% of the development time, and then firing at 100°C for 30 minutes.

[0183] For the above-described cured film, the transmittance of the cured film surface at 450 nm, 550 nm (λ), and 650 nm was measured using a SPECTROPHOTOMETER (CM-3700A, Konica Minolta). The measurement results are shown in Table 2 below. Among the measured transmittances of the cured film surface at 450 nm, 550 nm (λ), and 650 nm, the difference (T) between the maximum value (Tmax) and the minimum value (Tmin) was calculated and is shown together in Table 2 below.

[0184] The transmittance spectra of cured films with barrier patterns prepared using photosensitive resin compositions according to Example 2 and Comparative Examples 3 to 5 are shown in FIG. 1.

[0186] (2) Measurement of Reflectance (SCI, Specular Component Included)

[0187] A 5cm x 5cm glass substrate (Corning) was cleaned with neutral detergent and water, then dried. Blue PR forming blue pixels was spin-coated onto the glass substrate to a final film thickness of 1.0㎛, and the substrate was pre-fired at 100°C and dried for 2 minutes to remove the solvent. Then, an exposure dose of 100 mJ / cm² 2A substrate was fabricated by full-surface exposure, development for 150% of the development time, and subsequent firing at 100°C for 30 minutes. Each of the colored photosensitive resin compositions prepared in the above examples and comparative examples was spin-coated onto the corresponding Blue substrate to achieve a final film thickness of 1.0 μm, and the solvent was removed by pre-firing at 100°C and drying for 2 minutes. Then, an exposure dose of 100 mJ / cm² 2 A Blue / Black double-layer substrate was fabricated by full-surface exposure, development for 150% of the development time, and subsequent firing at 100°C for 30 minutes.

[0188] For the above-described manufactured Blue / Black double-film substrate, the reflectance of the cured film surface was measured using a SPECTROPHOTOMETER (CM-3700A, Konica Minolta), and the measurement results were classified according to the following criteria. The measurement results are shown in Table 2 below.

[0189] ◎ : Less than 5.0%

[0190] ○: 5.0% or more and less than 5.5%

[0191] △: 5.5% or more and less than 6.0%

[0192] X: 6.0% or more

[0194] (3) Measurement of Taper Angle

[0195] A 5cm x 5cm glass substrate (Corning) was washed with a neutral detergent and water, and then dried. Each of the colored photosensitive resin compositions prepared in the above examples and comparative examples was spin-coated onto the glass substrate to achieve a final film thickness of 1.0 μm, and the mixture was pre-fired at 100°C and dried for 2 minutes to remove the solvent. Then, an exposure dose of 100 mJ / cm² 2 A line pattern was exposed, and after developing for 150% of the development time, a cured film was produced by firing at 100°C for 30 minutes.

[0196] The cross-section of the line of the above-mentioned manufactured cured film was cut, and the Taper angle of the cross-section was measured using a scanning electron microscope (SU8100). The results were evaluated according to the following criteria and are shown in Table 2 below.

[0197] ◎: For cases of 30° or less

[0198] ○: In the case of exceeding 30° and not exceeding 40°

[0199] △: For cases exceeding 40° and up to 60°

[0200] X: If greater than 60°

[0202] (4) Measurement of optical density (OD, @550 nm)

[0203] For the above-described cured film, the optical density of the cured film surface was measured using a UV vis spectrometer (UV-1900, SHIMADZU). The measurement results are shown in Table 2 below.

[0205] Optical properties (1㎛) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 450nm transmittance (B) 22 24 27 18 18 28 30 64 21 17 4 550nm transmittance (G) 18 20 19 23 18 34 37 40 21 20 5 650nm transmittance (R) 22 23 27 19 28 47 44 30 51 32 4 T (Tmax-Tmin) 4 4 8 6 10 19 13 34 30 16 1 Pixel reflectance ◎ ◎ ○ ◎ ○ X X ○ △ X △ Taper angle ◎ ○ ○ ◎ ○ △ △ X ○ ○ X OD 0.6 0.6 0.7 0.5 0.6 0.5 0.4 0.3 0.6 0.6 1.3

[0206] Referring to Table 2 above, it was confirmed that the cured film of the barrier pattern prepared using the colored photosensitive resin compositions according to Examples 1 to 5 showed a difference (T) between the maximum transmittance and the minimum transmittance at 450 nm, 550 nm (λ), and 650 nm of 10 or less, and exhibited constant transmittance characteristics, particularly in the visible light region. On the other hand, the cured film of the barrier pattern prepared using the colored photosensitive resin compositions of Comparative Examples 1 to 5 showed a difference (T) between the maximum transmittance and the minimum transmittance exceeding 10, and thus failed to exhibit constant transmittance characteristics in the wavelength range of the visible light region. Consequently, in an organic light-emitting diode including a color filter, there was a problem in that the light source passing through the barrier was not transmitted consistently to each color filter. In addition, the cured film of the barrier pattern manufactured using the colored photosensitive resin composition of Comparative Example 6 had an OD value exceeding 1, resulting in low transmittance to a light source. Consequently, there was a problem in that it could not overcome the limitations of the conventional technology, as it could affect the color development of the color filter.

[0207] In addition, referring to Table 2 above, the cured film of the barrier pattern prepared using the colored photosensitive resin composition according to the example has a significantly reduced reflectance compared to the cured film prepared with the composition of the comparative example, resulting in a low specular reflectance to a light source and, accordingly, improved visibility.

[0208] On the other hand, the cured film prepared with the composition of the comparative example had poor reflectance characteristics or poor taper characteristics compared to the cured film prepared with the composition of the example, and had a problem that the optical density value was excessively high, affecting the color development of the color filter.

[0209] In summary, it was confirmed that when a cured film of a partition pattern is formed using the colored photosensitive resin composition of the present invention, an optical density (OD) of 1.0 or less can be provided, while exhibiting constant transmission characteristics in the wavelength range of the visible light region and reducing external light reflection, thereby providing a partition structure.

Claims

Claim 1 A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein a cured film prepared from the colored photosensitive resin composition has an optical density (OD) of 1.0 or less and a T value calculated by the following Formula 1 of 10 or less when the thickness of the cured film is 1 μm. [Formula 1] (In the above Equation 1, represents the maximum value among the transmittance (%) at λ, λ-100nm, and λ+100nm, and represents the minimum value among the transmittance (%) at λ, λ-100nm, and λ+100nm, and λ is a wavelength between 500nm and 570nm. Claim 2 A colored photosensitive resin composition according to claim 1, wherein when the thickness of the cured film is 1 μm, the T value calculated by Equation 1 is 8 or less. Claim 3 A colored photosensitive resin composition according to claim 1, wherein in Formula 1, λ is a wavelength of 550 nm. Claim 4 A colored photosensitive resin composition according to claim 1, wherein the colorant comprises a blue pigment. Claim 5 A colored photosensitive resin composition according to claim 1, wherein the blue pigment is one or more selected from CI pigment blue 15:6 and CI pigment blue 60. Claim 6 A colored photosensitive resin composition according to claim 1, characterized in that the colored photosensitive resin composition is for forming a barrier. Claim 7 A display partition structure manufactured from a colored photosensitive resin composition of any one of claims 1 to 6. Claim 8 A display device comprising the display partition structure of claim 7.

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