CN110268328B - Blue photosensitive resin composition, color filter and image display device manufactured by using the same - Google Patents
Blue photosensitive resin composition, color filter and image display device manufactured by using the same Download PDFInfo
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- CN110268328B CN110268328B CN201780086103.6A CN201780086103A CN110268328B CN 110268328 B CN110268328 B CN 110268328B CN 201780086103 A CN201780086103 A CN 201780086103A CN 110268328 B CN110268328 B CN 110268328B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Structural Engineering (AREA)
- Architecture (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a blue photosensitive resin composition, a color filter and an image display device manufactured by using the same, wherein the blue photosensitive resin composition comprises scattering particles, a blue colorant, a Cardo type binder resin as a binder resin, a photoinitiator, a photopolymerizable compound, a thermal curing agent and a solvent, wherein the thermal curing agent comprises more than one of a multifunctional alicyclic epoxy resin, a silane modified epoxy resin and a phenolic epoxy resin.
Description
Technical Field
The present invention relates to a blue photosensitive resin composition, a color filter and an image display device manufactured by using the composition.
Background
The color filter is a thin film type optical member capable of realizing a minute pixel unit by extracting three colors of red, green, and blue from white light, and the size of one pixel is about several tens to several hundreds of micrometers. Such a color filter has a structure in which a black matrix layer formed in a predetermined pattern on a transparent substrate to shield a boundary portion between pixels from light and a pixel portion formed by arranging three primary colors of a plurality of colors (usually, red (R), green (G), and blue (B)) in a predetermined order to form each pixel are sequentially stacked.
In recent years, as one of methods for realizing color filters, a pigment dispersion method using a pigment dispersion type photosensitive resin is applied. However, in the process of transmitting light irradiated from the light source through the color filter, a part of the light is absorbed by the color filter to lower the light efficiency, and there occurs a problem that the color reproducibility is lowered due to the characteristics of the pigment contained in the color filter.
In particular, as color filters are used in various fields including various image display devices, not only excellent pattern characteristics but also high color reproduction ratio and performances such as excellent high luminance and high contrast are required. In order to solve such problems, a method for manufacturing a color filter using a self-luminous photosensitive resin composition containing quantum dots has been proposed.
Korean laid-open patent No. 2013-0000506 relates to a display device, and discloses contents related to a display device including a color conversion section including: a plurality of wavelength converting particles for converting a wavelength of light; and a plurality of color filter particles for absorbing light of a predetermined wavelength band among the light.
However, the photosensitive resin compositions developed for the production of color filters to date have not sufficiently satisfied the effect of providing excellent viewing angles while having excellent pattern characteristics, heat resistance and stability.
Disclosure of Invention
Technical problem
The invention aims to provide a blue photosensitive resin composition which can prevent the efficiency reduction of blue pixels and reduce the manufacturing cost under the condition of not containing blue quantum dots, and a color filter and an image display device manufactured by the composition.
Technical scheme
The present invention provides a blue photosensitive resin composition comprising scattering particles, a blue colorant, a Cardo-based binder resin as a binder resin, a photoinitiator, a photopolymerizable compound, a thermal curing agent, and a solvent, wherein the thermal curing agent comprises at least one of a polyfunctional alicyclic epoxy resin, a silane-modified epoxy resin, and a novolac-type epoxy resin.
In addition, the present invention provides a color filter comprising a blue pattern layer composed of the above blue photosensitive resin composition.
In addition, the present invention provides an image display device comprising the above color filter and a light source emitting blue light.
Advantageous effects
The present invention includes the blue photosensitive resin composition, and therefore, the blue photosensitive resin composition has excellent heat resistance, does not yellow at high temperatures, and does not change the emission intensity. Further, there is provided a color filter capable of improving display defects by minimizing the occurrence of outgassing and removing disconnection of electrodes formed between pixels, which is free and is caused by back-taper during a developing process, in afterimages that may occur when a panel is operated. Further, a self-luminous color filter of high quality image quality having an excellent viewing angle can be provided.
Detailed Description
The present invention relates to a blue photosensitive resin composition. The blue photosensitive resin composition of the present invention contains scattering particles, a blue colorant, a Cardo-based binder resin as a binder resin, and a thermal curing agent, although it does not contain blue quantum dots, and thus can prevent the efficiency of blue pixels from being lowered and reduce the manufacturing cost.
Specifically, the blue photosensitive resin composition of the present invention may include scattering particles, a blue colorant, a Cardo-based binder resin as a binder resin, a photoinitiator, a photopolymerizable compound, a thermal curing agent, and a solvent. In particular, since the composition of the present invention includes one or more of a polyfunctional alicyclic epoxy resin, a silane-modified epoxy resin, and a novolac epoxy resin as the thermal curing agent, a color filter including a blue pattern layer manufactured using the blue photosensitive resin composition of the present invention can provide a color filter that is excellent in heat resistance, does not yellow at high temperature and does not have a change in emission intensity, and improves display defects by minimizing the amount of outgas generated, removing freedom from residual images that may occur during panel operation, and breaking of electrodes formed between pixels due to reverse taper during a developing process. Further, a color filter of high quality image quality having an excellent viewing angle, and more particularly, a self-luminous color filter and an image display apparatus including the same can be provided.
The structure of the present invention will be described in detail below.
Scattering particles
The scattering particles of the present invention are preferable in that they form an excellent fine pattern when the average particle diameter is 30 to 500 nm. In this case, when the average particle diameter falls within the above range, a sufficient scattering effect of incident light can be expected, and a problem of precipitation of scattering particles in the composition does not occur, and a self-light-emitting layer surface of uniform quality can be obtained.
The metal oxide may Be an oxide containing one metal selected from the group consisting of Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, In, and combinations thereof. More specifically, the metal oxide may be selected from the group consisting of Al2O3、SiO2、ZnO、ZrO2、BaTiO3、TiO2、Ta2O5、Ti3O5、ITO、IZO、ATO、ZnO-Al、Nb2O3SnO, MgO, and combinations thereof. If necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used.
The average particle diameter and the content of the scattering particles in the total composition are limited, so that the emission intensity of the color filter can be sufficiently increased.
In the present invention, the scattering particles may be contained in an amount of 0.5 to 35 wt%, preferably 1 to 30 wt%, with respect to the total weight of the blue photosensitive resin composition. If the content of the scattering particles is less than the above range, the desired emission intensity cannot be secured, whereas if the content of the scattering particles exceeds the above range, the effect of increasing the emission intensity is not more enhanced and the stability of the composition is lowered, so that the scattering particles are suitably used within the above range.
Blue colorant
Among The blue colorants of The present invention, specific examples of The blue pigment include compounds classified as pigments in The color index (published by The society of Dyers and Colourists), more specifically, pigments numbered by The following color index (c.i.), but The blue pigment is not necessarily limited to The pigment. Specifically, the blue pigment includes c.i. pigment blue 15:3, 15:4, 15:6, 16, 21, 28, and 76, and preferably includes one or more selected from the group consisting of c.i. pigment blue 15:3, pigment blue 15:6, and pigment blue 16.
The blue colorant of The present invention may further contain a blue dye, and as The blue dye, compounds classified as dyes in The color index (published by The society of Dyers and Colourists) or known dyes described in The dyeing manual (Dyers) can be cited.
Specific examples of the above-mentioned further usable dyes,
as a c.i. solvent dye,
examples thereof include c.i. solvent blue 5, 35, 36, 37, 44, 45, 59, 67, and 70, and more preferably include one or more of c.i. solvent blue 35, 36, 44, 45, and 70.
Further, as the c.i. acid dye,
examples of the c.i. acid blue include c.i. acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, 335, and 340, and more preferably include one or more of c.i. acid blue 80 and 90.
In addition, as the c.i. direct dye,
c.i. direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, and 293, etc. can be cited.
Examples of the c.i. medium blue include c.i. medium blue 1,2,3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84.
The blue dyes may be used independently or in combination of two or more.
The blue colorant of the present invention may further comprise a violet colorant as an additional colorant. The violet colorant may include one or more of a violet pigment and a violet dye, and specific examples of the violet pigment include c.i. pigment violet 1, 14, 19, 23, 29, 32, 33, 36, 37, and 38, and among them, c.i. pigment violet 23 is more preferably included.
Specific examples of the violet dye include, but are not limited to, c.i. solvent violet, c.i. acid violet, and c.i. mordant violet.
Specifically, the c.i. solvent violet includes c.i. solvent violet 8, 9, 13, 14, 36, 37, 47, and 49, and more preferably c.i. solvent violet 13. Examples of the c.i. acid violet include c.i. acid violet 6B, 7, 9, 17, 19, and 66, and c.i. acid violet 66 is more preferably contained. Examples of the c.i. direct violet include c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, and 104.
Further, c.i. medium violet 1,2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 and the like are exemplified.
In the present invention, the blue colorant may be included in an amount of 0.5 to 40% by weight, preferably 0.5 to 30% by weight, relative to the total weight of the blue photosensitive resin composition. When the content of the blue colorant satisfies the above range, reflection of external light can be suppressed, color emission intensity can be efficiently exhibited, and viscosity stability can be ensured.
Adhesive resin
The binder resin of the present invention comprises a Cardo-based binder resin. The Cardo-based binder resin has reactivity and alkali solubility with the action of light or heat, and functions as a dispersion medium for a coloring material. The Cardo-based binder resin contained in the blue photosensitive resin composition of the present invention functions as a binder resin for the scattering particles, and is not limited as long as it is a resin that can be dissolved in an alkaline developer used in a developing step for producing a color filter.
The Cardo-based binder resin of the present invention is prepared by reacting one or more of the compounds represented by the following chemical formulas 1-1 and 1-2 with at least one of an acid anhydride and an acid dianhydride.
[ chemical formula 1-1]
[ chemical formulas 1-2]
In the above chemical formula 1-1 or chemical formula 1-2, R1、R2、R3And R4Are each independently
Wherein X is hydroxy, R5Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
In the present invention, the compound represented by the above chemical formula 1-1 is synthesized from the compound represented by the following chemical formula 2-1, and the compound represented by the chemical formula 1-2 can be synthesized using the compound represented by the chemical formula 2-2.
In the present invention, the compound represented by the above chemical formula 1-1 is synthesized from the compound represented by the following chemical formula 2-1, and the compound represented by the chemical formula 1-2 can be synthesized using the compound represented by the chemical formula 2-2.
[ chemical formula 2-1]
[ chemical formula 2-2]
Specifically, the compound represented by the above chemical formula 1-1 may be one or more of the compounds represented by the above chemical formulas 1-1-1 and 1-1-2, and the compound represented by the above chemical formula 1-2 may be one or more of the compounds represented by the above chemical formulas 1-2-1 and 1-2-2.
[ chemical formula 1-1-1]
[ chemical formulas 1-1-2]
[ chemical formula 1-2-1]
[ chemical formula 1-2-2]
Can be prepared by reacting a compound selected from the group consisting of 9,9-bis (3-cinnamic diester) fluorene (9,9-bis (3-cinnamylamino diester) fluorene), 9-bis (3-cinnamon oil,4-hydroxyphenyl) fluorene (9,9-bis (3-cinnamylamino, 4-hydroxyphenyl) fluorene), 9-bis (glycidyl methacrylate ether) fluorene (9,9-bis (glycidyl methacrylate ether) fluorene), 9-bis (3,4-dihydroxyphenyl) fluorene diesteramide (9,9-bis (3,4-dihydroxyphenyl) fluorene diesteramide), 3,6-diglycidyl methacrylate ether spiro (fluorene-9, 9-xanthene) (3,6-diglycidyl methacrylate ether), allyl-fluorene-9, 9-diol (9-allyl-9-xanthene) (9,9-bis (3, 9-diglycidyl ether), 4-hydroxyphenyl fluorene) (9,9-bis (3-allyl, 4-hydroxyphenylfluoride)), 9-bis (4-allyloxyphenyl) fluorene (9,9-bis (4-allyloxyphenyl) fluoride) and 9,9-bis (3,4-methacrylic diester) fluorene (9,9-bis (3,4-methacrylic di ester) fluoride) are reacted with at least one selected from the group consisting of maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylenetetrahydrophthalic anhydride, chlorendic anhydride and methyltetrahydrophthalic anhydride as acid anhydrides or selected from the group consisting of pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and biphenyl ether tetracarboxylic dianhydride as acid dianhydrides to prepare the above-mentioned Cardo-based adhesive resin, but is not limited thereto.
The present invention may further include an acrylic alkali-soluble resin as the binder resin. Examples of the acrylic alkali-soluble resin include copolymers of a carboxyl group-containing monomer and another monomer copolymerizable with the carboxyl group-containing monomer. Examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated polycarboxylic acids such as unsaturated dicarboxylic acids and unsaturated tricarboxylic acids, and unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polycarboxylic acid may be a mono (2-acryloyloxyalkyl) ester thereof, and examples thereof include mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. The unsaturated polycarboxylic acid may also be a mono (meth) acrylate of a dicarboxylic polymer at both ends thereof, and examples thereof include ω -carboxy polycaprolactone monoacrylate, ω -carboxy polycaprolactone monomethacrylate and the like. These carboxyl group-containing monomers may be used either individually or as a mixture of two or more thereof. Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and indene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, isopropyl acrylate, isobutyl acrylate, butyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxypropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof, Unsaturated carboxylic acid esters such as dicyclopentadienyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; aminoalkyl esters of unsaturated carboxylic acids such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; and macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. These monomers may be used either individually or as a mixture of two or more thereof. In particular, as the other monomer copolymerizable with the above carboxyl group-containing monomer, a bulky monomer such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton tends to lower the relative dielectric constant, and therefore, it is preferable.
The Cardo-based binder resin or acrylic alkali-soluble resin as the present invention preferably has an acid value in the range of 20 to 200(KOH mg/g). If the acid value is within the above range, the solubility in the developer is increased, the non-exposed portion is easily dissolved, the sensitivity is increased, and as a result, the film remaining ratio (film remaining ratio) can be improved by remaining the non-exposed portion during the development of the pattern of the exposed portion. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the acrylic polymer, and can be usually determined by titration using an aqueous potassium hydroxide solution. Further, it is preferable that the Cardo-based binder resin and/or the acrylic alkali-soluble resin have a polystyrene-equivalent weight average molecular weight (hereinafter, simply referred to as "weight average molecular weight") of 2,000 to 200,000, preferably 3,000 to 100,000, as measured by gel permeation chromatography (GPC; with tetrahydrofuran as an eluting solvent). When the molecular weight is within the above range, the hardness of the coating film tends to be high, the residual film ratio tends to be high, and the unexposed area tends to have excellent solubility in a developer and to improve the resolution.
The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the Cardo-based binder resin and/or acrylic alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.5 to 6.0. It is preferable that the molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] is from 1.5 to 6.0 because the developability is excellent.
In the present invention, the binder resin may be included in an amount of 1.0 to 50% by weight, and preferably 5.0 to 30% by weight, relative to the total weight of the blue photosensitive resin composition. If the content of the binder resin is within the above range, the solubility in the developer is sufficient, development residue is less likely to occur in the non-pixel portion on the substrate, and the film reduction in the pixel portion where the exposed portion is less likely to occur during development tends to be excellent, and the leakage property in the non-pixel portion tends to be excellent.
Photopolymerizable compound
The photopolymerizable compound contained in the blue photosensitive resin composition of the present invention is a compound polymerizable by light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, difunctional monomers, and other polyfunctional monomers. Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. Specific examples of the bifunctional monomer include 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of the other polyfunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Among them, a polyfunctional monomer having two or more functions is preferably used.
The photopolymerizable compound may be included at 0.5 to 20 wt%, preferably 1.0 to 10 wt%, with respect to the total weight of the blue photosensitive resin composition. When the photopolymerizable compound is contained in the above range, the sensitivity is not lowered, the adhesiveness of the photosensitive resin layer is too strong and the film strength is insufficient, and the pattern disappearance problem does not occur at the time of development.
Photoinitiator
The photoinitiator used in the present invention preferably contains an acetophenone compound, which enhances the sensitivity of the photosensitive resin composition and improves the productivity. Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylphenylsulfanyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and oligomers of 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl ] propan-1-one, preferred examples thereof include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and the like. Further, photopolymerization initiators other than the acetophenones described above may be used in combination. Examples of the photopolymerization initiator other than acetophenones include an active radical generator, a sensitizer, an acid generator, and the like, which generate active radicals by irradiation with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and triazine compounds. Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone-based compound include benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3', 4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and the like. Examples of the active radical generators include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2-bis (o-chlorophenyl) -4, 4', 5 ' -tetraphenyl-1, 2' -biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9, 10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds. Examples of the acid generator include onium salts such as 4-hydroxyphenyl dimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl toluenesulfonate and benzoin toluenesulfonate. In addition, as the active radical generating agent, a compound which generates an active radical and an acid simultaneously is also present among the above compounds, and for example, a triazine-based photopolymerization initiator may also be used as the acid generator.
In the present invention, the photoinitiator may be included in an amount of 0.1 to 15 wt%, preferably 0.4 to 10 wt%, with respect to the total weight of the blue photosensitive resin composition. When the content of the photoinitiator is within the above range, the blue photosensitive resin composition tends to have high sensitivity, and a pixel portion formed using the composition tends to have excellent strength and surface smoothness of the pixel portion.
In addition, the present invention may further comprise a photopolymerization initiation aid. The photopolymerization initiation assistant may be used in combination with a photopolymerization initiator, and is a compound used for promoting polymerization of a photopolymerizable compound whose polymerization is initiated by the photopolymerization initiator. Examples of the photopolymerization initiation aid include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4' -bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4' -bis (diethylamino) benzophenone, and 4,4' -bis (ethylmethylamino) benzophenone, and among them, 4' -bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene compound include 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, and 2-ethyl-9, 10-diethoxyanthracene. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. The photopolymerization initiator (D) may be used alone or in combination of two or more. Further, as the photopolymerization initiation assistant, commercially available products may be used, and examples of the commercially available photopolymerization initiation assistant include "EAB-F" (manufactured by UK Seiko chemical Co., Ltd.).
When these photopolymerization initiation aids are used, the amount of the polymerization initiation aid used is usually 10 moles or less, preferably 0.01 to 5 moles per 1 mole of the photopolymerization initiator. If the amount of the polymerization initiator is within the above range, the sensitivity of the blue photosensitive resin composition tends to be further improved and the productivity of a color filter formed using the composition tends to be improved, which is preferable.
Thermal curing agent
The heat-curing agent contained in the present invention plays a role in enhancing the deep curing and mechanical strength of the coating film. The thermal curing agent of the present invention may contain one or more of a polyfunctional alicyclic epoxy resin, a silane-modified epoxy resin, and a novolac-type epoxy resin.
The above multifunctional alicyclic epoxy resin is prepared by polymerizing a diene compound, and according to one embodiment, may be an alicyclic epoxy resin including a compound represented by chemical formula 3 or 4.
[ chemical formula 3]
In the above chemical formula 3, n, m and l are integers of 1 to 20.
[ chemical formula 4]
<3, 4-epoxycyclohexyl-3, 4-epoxycyclohexyl formate >
The phenol epoxy resin may be cresol novolac, and may be an epoxy resin of the following chemical formula 5 according to an embodiment.
[ chemical formula 5]
In the chemical formula 5, o is an integer of 1 to 20.
Examples of commercially available novolac epoxy resins include p-cresol novolac epoxy resin (manufactured by Sumiepoxy ESCN195 XL-Sumitomo chemical industry Co., Ltd.), alicyclic epoxy compound "CEL-2021", alicyclic solid epoxy resin "EHPE-3150", epoxidized polybutadiene "PB 3600", flexible aliphatic epoxy compound "CEL-2081", and lactone-modified epoxy resin "PCL-G" (manufactured by Daiiseo chemical industry Co., Ltd.). In addition, Celloxide 2000, EPOLED GT-3000, and GT-4000 (both manufactured by Dailuo chemical Co., Ltd.) can be cited. Among them, ESCN-195XL, which is a novolac type epoxy resin, is the most excellent in curability, and "CEL-2021P" and "EHPE-3150" are the most excellent in curability among alicyclic epoxy resins. These compounds may be used alone, or two or more of them may be used in combination, or may be combined with other compounds shown later.
The silane modified epoxy resin is a reactant of hydroxyl-containing epoxy resin and alkoxy silane. Examples of the hydroxyl group-containing epoxy resin include bisphenol type epoxy resins, phenol type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, linear aliphatic epoxy resins, biphenyl type epoxy resins, and the like. Among them, bisphenol type epoxy resins and novolac type epoxy resins are preferably used. The bisphenol epoxy resin can be obtained by reacting a bisphenol with a halogenated epoxy compound such as chloromethyl oxirane or α -methyl chloromethyl oxirane. Examples of the bisphenols include reaction products of phenol or 2, 6-dihalophenol with aldehydes or ketones such as formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, and benzophenone, oxidation products by a peracid of dihydroxythiophenyl, and etherification reaction products between hydroquinones. Among these bisphenol type epoxy resins, bisphenol type epoxy resins obtained by using bisphenol a, bisphenol S, bisphenol F or hydrogen additives thereof as bisphenols are most widely used, and are preferred. The bisphenol epoxy resin has a hydroxyl group capable of reacting with an alkoxysilane described later. The hydroxyl group does not need to have all molecules constituting the bisphenol epoxy resin, and the hydroxyl group is present as the bisphenol epoxy resin as a whole. For example, although the bisphenol a type epoxy resin is represented by the following chemical formula 1, a substance in which m is 1 or more, or a substance in which m is O may be contained.
[ chemical formula 6]
In the above chemical formula 6, q is an integer of 1 to 34.
Such a bisphenol epoxy resin can be used as a phosphorus-modified bisphenol epoxy resin by reacting a phosphorus compound, for example.
For example, the novolac-type epoxy resin can be obtained by reacting a halogenated epoxy compound with a phenol novolac resin or a cresol novolac resin.
For example, the above-mentioned glycidyl ester type epoxy resin can be obtained by reacting chloromethyl oxirane with other alkali acids such as phthalic acid.
For example, the glycidyl amine type epoxy resin can be obtained by reacting polyamines such as diaminodiphenylmethane and isocyanuric acid with chloromethyloxirane.
For example, the linear aliphatic epoxy resin and the aliphatic epoxy resin can be obtained by treating olefins with a peracid such as peracetic acid.
For example, the biphenyl type epoxy resin can be obtained by reacting bisphenols with chloromethyl oxirane.
The preferred value of the epoxy equivalent of the hydroxyl group-containing epoxy resin differs depending on the structure of the hydroxyl group-containing epoxy resin. The hydroxyl group-containing epoxy resin can be suitably selected and used according to the purpose. In general, when the hydroxyl group-containing epoxy resin component having an excessively small epoxy equivalent is used as a protective film, the adhesion to a substrate may be reduced, and therefore the epoxy equivalent of the hydroxyl group-containing epoxy resin component is preferably 180 or more.
In addition, when a hydroxyl group-containing epoxy resin component having an excessively large epoxy equivalent is used, gelation may occur during the reaction with alkoxysilane, and therefore the epoxy equivalent of the hydroxyl group-containing epoxy resin component is preferably 5,000 or less.
More preferably, the epoxy equivalent weight is 200 to 400.
Further, as the above alkoxysilane, an alkoxysilane used in a sol-gel method can be generally used.
For example, compounds represented by chemical formula 7 or their partial condensates are cited.
[ chemical formula 7]
R6pSi(OR7)4-p
In chemical formula 7, p represents an integer of 0 or 1, R6 represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms, or an unsaturated aliphatic residue having 2 to 6 carbon atoms, which may have a functional group directly attached to a carbon atom, R7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a plurality of R7 s are the same or different, respectively.
More specifically, examples of the functional group of R6 include a vinyl group, a mercapto group, an epoxy group, and a glycidoxy group.
The "partial condensate" refers to a product obtained by condensing a part of the epoxy groups in the alkoxysilane represented by the above chemical formula 7. Such a partial condensate can be obtained by decomposing the above alkoxysilane with water in the presence of an acid or a base and water.
Specific examples of such alkoxysilanes include: tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and the like; trialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3, 4-epoxycyclohexylethyltrimethoxysilane, 3, 4-epoxycyclohexylethyltriethoxysilane, etc.; or partial condensates thereof, and the like.
Among them, partial condensates of tetramethoxysilane or alkyltrimethoxysilane represented by the following chemical formula 8 are preferable.
[ chemical 8]
(in chemical formula 8, R3A methoxy group or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 7).
The average molecular weight of the partial condensate of tetramethoxysilane or alkyltrimethoxysilane represented by the above chemical formula 8 is preferably about 260 to 2,000, more preferably about 260 to 890. This partial condensate of tetramethoxysilane or alkyltrimethoxysilane is preferable from the viewpoint of reaction operation because when it reacts with the hydroxyl group-containing epoxy resin component, the unreacted alkoxysilane component evaporates together with methanol and does not flow out to the outside of the system. Furthermore, toxicity as expressed by the corresponding monomer does not exist in such partial condensates and is therefore preferred.
In chemical formula 8, the value (n) of the average number of repeating units is preferably 11 or less, and more preferably 7 or less. When the value is more than 11, the solubility is poor and the compound is not easily dissolved in the hydroxyl group-containing epoxy resin or the organic solvent, and therefore the reactivity with the hydroxyl group-containing epoxy resin tends to be low.
The silane-modified epoxy resin is obtained by dealcoholization condensation reaction of the above hydroxyl-containing epoxy resin and alkoxysilane. The ratio of the hydroxyl group-containing epoxy resin to the alkoxysilane is not particularly limited as long as it is the same as the ratio of the alkoxy groups actually remaining in the obtained silane-modified epoxy resin, but it is preferable to set the silicon-equivalent mass of the alkoxysilane/the mass of the hydroxyl group-containing epoxy resin (mass ratio) to a range of 0.01 to 3.
However, when the hydroxyl group-containing epoxy resin is a high molecular weight resin having an epoxy equivalent of about 400 or more, the solution may be highly viscous or gelated due to the progress of the dealcoholization reaction, and therefore such a problem can be overcome as follows.
In order to increase one of the hydroxyl equivalent of the hydroxyl-containing epoxy resin and the alkoxy equivalent of the alkoxysilane, the equivalent ratio is preferably adjusted to less than 1 or greater than 1. In particular, it is preferable to adjust the equivalent ratio to less than 0.8 or 1.2 or more. Among them, the production is preferably 1.2 or more.
② the dealcoholization reaction is stopped in the middle of the reaction to prevent the viscosity from increasing or the gelation. For example, a method of adjusting the amount of methanol removed by distillation in the reaction system by setting the reaction system to a reflux system at the time of gradually increasing the viscosity, or a method of cooling the reaction system to terminate the reaction, or the like can be employed.
For example, the silane-modified epoxy resin is produced by adding the above components, and performing dealcoholization condensation reaction while distilling off the alcohol generated by heating. The reaction temperature is preferably 50 ℃ to 130 ℃, more preferably 70 ℃ to 110 ℃, and the total reaction time is preferably 1 to 15 hours. Preferably, in order to prevent the polycondensation reaction of the alkoxysilane itself, the reaction is carried out under virtually anhydrous conditions. In addition, in order to shorten the reaction time, the reaction may be carried out under reduced pressure in a range where the hydroxyl group-containing epoxy resin is not evaporated.
In addition, in the dealcoholization condensation reaction, a catalyst having no ring-opened oxirane ring among conventionally known catalysts may be used in order to accelerate the reaction. Examples of the catalyst include: metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, cadmium, manganese, and the like; oxides, organic acid salts, halides, alkoxides, and the like of these metals. Among them, organotin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate, tin octylate and the like are effective.
Further, the above reaction may be carried out in a solvent. The solvent is not particularly limited as long as it is an organic solvent that dissolves the hydroxyl-containing epoxy resin and the alkoxysilane and does not react with them. Examples of such an organic solvent include aprotic polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, and methyl ethyl ketone.
Commercially available products preferably used as the silane-modified epoxy resin include, for example, those sold under the trade names COMPOSERAN E-101, E-102, E-201, E-202, E-211 and E-212 manufactured by Ishikawa chemical Co., Ltd.
The silane-modified epoxy resin is contained in an amount of 0.1 to 30 wt% based on the solid powder in the photosensitive resin composition. When the silane-modified epoxy resin is added in an amount less than the above range, chemical resistance is lowered, and when the silane-modified epoxy resin is added in an excessive amount, there is a problem in heat resistance and development speed.
The thermosetting agent contained in the blue photosensitive resin composition of the present invention reacts with the carboxyl group in the binder resin to enhance the crosslinking of the binder resin during the heat treatment of the pixel coating after development in the process of manufacturing a color filter (usually at 180 to 250 ℃ or lower, preferably at 200 to 230 ℃ for 5 to 40 minutes, more preferably 10 to 35 minutes), thereby improving the hardness of the coating and further improving the performance of the color filter.
In the present invention, the heat curing agent may be included in an amount of 0.1 to 20 wt%, preferably 0.1 to 10 wt%, based on the total weight of the blue photosensitive resin composition. When the thermosetting agent is contained within the above range, the chemical resistance is excellent and no problem occurs in heat resistance and development speed.
Solvent(s)
The solvent contained in the blue photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of blue photosensitive resin compositions can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ -butyrolactone. Among the solvents, from the viewpoint of coating properties and drying properties, preferred are organic solvents having a boiling point of 100 to 200 ℃ among the solvents, more preferred are ester-linked solvents such as alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and still more preferred are propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. The solvents mentioned above may be used either individually or in combination of two or more.
In the present invention, the solvent may be contained in an amount of 10 to 85% by weight, preferably 15 to 85% by mass, relative to the total weight of the blue photosensitive resin composition. If the solvent content is within the above range, the coating properties tend to be excellent when the coating is performed by a coating device such as a roll coater, a spin coater, a slit coater (sometimes referred to as a die coater), or a spray coater, and therefore, the solvent content is preferably within the above range.
Additive agent
The blue pattern layer metal oxide photosensitive resin composition of the present invention may further contain other high molecular compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-coagulants, and the like, as necessary.
Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
As the pigment dispersant, commercially available surfactants can be used, and examples thereof include silicon-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric and other surfactants. They may be used each alone or in combination of two or more.
Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl diethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines, and also include, as trade names, KP (manufactured by shin-Etsu chemical Co., Ltd.), POLYFLOW (manufactured by Synken chemical Co., Ltd.), EFTOP (manufactured by Tokheimproduct Co., Ltd.), MEGAFAC (manufactured by Dajapan ink chemical Co., Ltd.), Flourad (manufactured by Sumiton (manufactured by Asahi Karl), Surflon (manufactured by Asahi Nitro Co., Ltd.), SOLSPERSE (manufactured by Rijiekang Co., Ltd.), EFKA (manufactured by EFKA chemical Co., Ltd.), and PB 821 (manufactured by Kudzein Co., Ltd.).
Examples of the adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like. Specific examples of the antioxidant include 2,2' -thiobis (4-methyl-6-tert-butylphenol) and 2, 6-di-tert-butyl-4-methylphenol.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the anti-gelling agent include sodium polyacrylate and the like.
The skilled person can appropriately additionally use the above-mentioned additives within a range not to hinder the effect of the present invention. For example, the additive may be used in an amount of 0.01 to 10 wt%, preferably 0.1 to 10 wt%, and more preferably 0.1 to 5 wt% with respect to the total amount of the metal oxide photosensitive resin composition, but is not limited thereto.
The metal oxide photosensitive resin composition of the present invention can be prepared, for example, by the following method. The scattering particles are mixed with a solvent in advance, and dispersed by a bead mill or the like until the average particle diameter reaches 30-500 nm. In this case, a dispersant may be further used as needed, and a part or all of the binder resin may be added. The dispersion obtained (hereinafter, also referred to as "mill base") is further added with an excess of a binder resin, a photopolymerizable compound, a photopolymerization initiator, other components used as needed, and a solvent added as needed at a predetermined concentration, thereby obtaining a desired metal oxide photosensitive resin composition.
<Color filter and image display device>
Still another embodiment of the present invention relates to a color filter including a blue pattern layer containing a cured product of the blue photosensitive resin composition for forming the blue pattern layer.
The color filter of the present invention is prepared by using the blue photosensitive resin composition for forming a blue pattern layer instead of blue quantum dots, and thus has advantages that the manufacturing cost can be reduced, and the efficiency of blue pixels can be prevented from being lowered and the viewing angle is excellent without including blue quantum dots.
The color filter includes a substrate and a blue pattern layer formed on the substrate.
The substrate may be a substrate of the color filter itself, or may be a portion where the color filter is located in a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyether sulfone (PES), Polycarbonate (PC), or the like.
The blue pattern layer is a layer containing the metal oxide photosensitive resin composition of the present invention, and may be a layer formed by applying the metal oxide photosensitive resin composition for forming the blue pattern layer and performing exposure, development and heat curing in a predetermined pattern, and the pattern layer may be formed by performing a method generally known in the art.
In still another embodiment of the present invention, the color filter may further include one or more selected from the group consisting of a red pattern layer and a green pattern layer.
In yet another embodiment of the present invention, the red pattern layer or the green pattern layer must include quantum dots and may additionally include scattering particles. Specifically, the color filter of the present invention may include a red pattern layer including red quantum dots or a green pattern layer including green quantum dots, which may include scattering particles. The red pattern layer or the green pattern layer may emit red light or blue light, respectively, by a light source that emits blue light, which will be described later.
In still another embodiment of the present invention, the scattering particles contained in the red pattern layer or the green pattern layer may contain a metal oxide having an average path of 30 to 500nm, and the contents related to the scattering particles and the metal oxide can be applied to the contents related to the scattering particles and the metal oxide contained in the metal oxide photosensitive resin composition of the present invention.
In the present invention, the form, structure and content of the quantum dots included in the red pattern layer or the green pattern layer are not limited, and quantum dots generally used in the art may be applied.
The color filter including the substrate and the pattern layer may further include a partition wall formed between the patterns, and may further include a black matrix, but is not limited thereto.
Still another embodiment of the present invention relates to an image display device including the color filter and a light source emitting blue light. For example, an image display device of the present invention includes a color filter including a blue pattern layer of a cured product of the metal oxide photosensitive resin composition and a light source emitting blue light.
The color filter of the present invention can be applied not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.
In the case where the above-described image display device includes the color filter including the blue pattern layer of the present invention and the above-described light source, there is an advantage of having excellent emission intensity or viewing angle. In addition, since the blue pattern layer included in the color filter of the present invention does not include blue quantum dots, there is an advantage in that an image display device with low manufacturing costs can be manufactured.
Hereinafter, the present specification will be described in detail with reference to examples. However, the embodiments in the present specification may be modified into other various forms, and the scope of the present specification should not be construed as being limited to the embodiments described in detail below. The embodiments of the present description are provided to more fully describe the present description to those of ordinary skill in the art. In the following, unless otherwise specified, "%" and "part(s)" representing the content are based on weight.
Synthesis example: synthesis of Binder resin
Preparation example 1: alkali soluble resin
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen gas inlet tube was prepared, and 7.8g (0.20 mol) of benzylmaleimide, 43.2g (0.30 mol) of acrylic acid, 118.0g (0.50 mol) of vinyl toluene, 4g of t-butylperoxy-2-ethylhexanoate, and 40g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) were added to the flask as a monomer dropping funnel, followed by stirring and mixing, and 6g of n-dodecanethiol and PGMEA24g were added to the flask as a chain transfer agent dropping tank, followed by stirring and mixing. Thereafter, 395g of PGMEA was introduced into the flask, and after the atmosphere in the flask was replaced with nitrogen gas from the air, the temperature of the flask was raised to 90 ℃ while stirring. Subsequently, the monomer and the chain transfer agent were dropped from the dropping funnel. During the dropping, the temperature was raised to 110 ℃ for 3 hours after 1 hour while maintaining 90 ℃ for 2 hours, and then introduced into a gas introduction tube to start bubbling of an oxygen/nitrogen (5/95 (v/v) mixed gas. Then, 28.4g of glycidyl methacrylate [ (0.10 mol%) (33 mol% based on the carboxyl group of acrylic acid used in the present reaction) ], 0.4g of 2,2' -methylenebis (4-methyl-6-tert-butylphenol) and 0.8g of triethylamine were placed in a flask, and the reaction was continued at 110 ℃ for 8 hours to obtain a resin A having a solid acid value of 70 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 16,000, and the molecular weight distribution (Mw/Mn) was 2.3.
Preparation example 2: synthesis of Compound of chemical formula 1-1-1
In a 3000ml three-necked round-bottomed flask, 364.4g of 3', 6' -dihydroxyspiro (fluorene-9,9 '-xanthene) (3', 6 '' -dihydroyspiro (fluoroene-9, 9-xanthene) of chemical formula 2-1 and 0.4159g of tert-butylammonium bromide were mixed, and 2359g of epichlorohydrin was added thereto, heated to 90 ℃ and allowed to react, analyzed by liquid chromatography, if the 3', 6 ' -dihydroxyspiro (fluorene-9,9 ' -xanthene) is completely consumed, cooled to 30 c and slowly added with 50% aqueous NaOH solution (3 equivalents), analyzed by liquid chromatography, extracted with dichloromethane and washed 3 times with water if epichlorohydrin is completely consumed, the organic layer was then dried with magnesium sulfate and then dichloromethane was distilled under reduced pressure, and dichloromethane and methanol were used in a mixing ratio of 50:50 and recrystallization was performed.
After mixing 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2, 6-diisobutylphenol and 2.2 equivalents of acrylic acid, 24.89g of propylene glycol monomethyl ether acetate as a solvent was added and mixed. Blowing air into the reaction solution at a rate of 25ml/min and heating to a temperature of 90-100 ℃ to dissolve the air. The reaction solution was heated to 120 ℃ in a cloudy state to completely dissolve the reaction solution. If the solution became transparent and the viscosity became high, the acid value was measured and stirring was carried out until the acid value was less than 1.0 mgKOH/g. It took 11 hours until the acid value reached the target value (0.8). After the reaction was completed, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of chemical formula 1-1-1.
[ chemical formula 1-1-1]
Preparation example 3: synthesis of Compound of chemical formula 1-2-1
In a 3000ml three-necked round-bottomed flask, 364.4g of 4,4'- (9H-xanthene-9,9-diyl) diphenol (4,4' - (9H-xanthene-9,9-diyl) diphenol) and 0.4159g of tert-butyl ammonium bromide were mixed, and after addition of 2359g of epichlorohydrin, the mixture was heated to 90 ℃ and allowed to react. When 4,4' - (9H-xanthene-9,9-diyl) diphenol was completely consumed as analyzed by liquid chromatography, it was cooled to 30 ℃ and 50% aqueous NaOH (3 equivalents) was slowly added. Analysis was performed by liquid chromatography, and if epichlorohydrin was completely consumed, extraction with dichloromethane was followed by washing with water 3 times, then the organic layer was dried with magnesium sulfate and then dichloromethane and methanol were distilled under reduced pressure, and recrystallization was performed using dichloromethane and methanol at a mixing ratio of 50: 50. After mixing 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2, 6-diisobutylphenol and 2.2 equivalents of methacrylic acid, 24.89g of propylene glycol monomethyl ether acetate as a solvent was added and mixed. Blowing air into the reaction solution at a rate of 25ml/min and heating to a temperature of 90-100 ℃ to dissolve the air. The reaction solution was heated to 120 ℃ in a cloudy state to completely dissolve the reaction solution. If the solution became transparent and the viscosity became high, the acid value was measured and stirring was carried out until the acid value was less than 1.0 mgKOH/g. It took 11 hours until the acid value reached the target value (0.8). After the reaction was completed, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of chemical formula 1-2-1.
[ chemical formula 1-2-1]
Preparation example 4: synthesis of Cardo-based adhesive resin (C-1)
After adding and dissolving 600g of propylene glycol monomethyl ether acetate to 307.0g of the compound of chemical formula 1-1-1 of preparation example 2, 78g of biphenyltetracarboxylic dianhydride and 1g of tetraethylammonium bromide were mixed and reacted at 110 to 115 ℃ for 4 hours while slowly raising the temperature. After confirming the disappearance of the acid anhydride group, 38.0g of 1,2,3, 6-tetrahydrophthalic anhydride was mixed and reacted at 90 ℃ for 6 hours to polymerize a Cardo-based binder resin. The disappearance of the anhydrate was confirmed by IR spectroscopy. The weight average molecular weight is 3500.
Preparation example 5: synthesis of Cardo-based adhesive resin (C-2)
After adding and dissolving 600g of propylene glycol monomethyl ether acetate to 307.0g of the compound of chemical formula 1-2-1 of preparation example 3, 78g of benzenetetracarboxylic dianhydride and 1g of tetraethylammonium bromide were mixed and reacted at 110 to 115 ℃ for 4 hours while slowly raising the temperature. After confirming the disappearance of the acid anhydride group, 38.0g of 1,2,3, 6-tetrahydrophthalic anhydride was mixed and reacted at 90 ℃ for 6 hours to polymerize a Cardo-based binder resin. The disappearance of the anhydrate was confirmed by IR spectroscopy. The weight average molecular weight was 4500.
The device comprises the following steps: HLC-8120GPC (manufactured by Tosoh corporation)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 deg.C
Mobile phase solvent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 50 μ L
A detector: RI (Ri)
And (3) measuring the concentration of the sample: 0.6% by weight (solvent ═ tetrahydrofuran)
Calibration standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corp.)
The ratio of the weight average molecular weight and the number average molecular weight obtained above was defined as a molecular weight distribution (Mw/Mn).
Examples 1 to 32 and comparative examples 1 to 8: preparation of blue photosensitive resin composition
Blue photosensitive resin compositions of examples 1 to 32 and comparative examples 1 to 8 were prepared according to the compositions of tables 1 to 6 below (table 1 shows scattering particles, table 2 shows blue and violet color materials, tables 3 to 5 show compositions of examples, and table 6 shows composition compositions and contents of comparative examples).
[ Table 1]
[ Table 2]
| Species of | Product name | Manufacturing company | |
| B-1 | B15:6 | Fastogen Blue EP-7S | DIC |
| B-2 | B15:4 | Fastogen Blue 5424 | DIC |
| B-3 | B15:3 | Heliogen Blue L 7072 D | BASF |
| B-4 | B16 | Pigment Blue 16 | CPMA |
| V-1 | V23 | Fastogen Super Violet 140V | DIC |
[ Table 3]
A. Scattering particles (see Table 1)
B. Blue/purple color material (refer to Table 2)
C. Alkali-soluble resin: cardo resin (chemical formula C-1)/Cardo resin (chemical formula C-2)/acrylic alkali soluble resin
D. Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kabushiki Kaisha)
E. Photopolymerization initiator: irgaqure-907 (manufactured by BASF corporation)
F. Solvent: propylene glycol monomethyl ether acetate
G. Thermal curing agent: alicyclic epoxy resin (chemical formula 3/chemical formula 4)/novolac epoxy resin (chemical formula 5)/silane-modified epoxy resin (chemical formula 6/chemical formula 7)
[ Table 4]
A. Scattering particles (see Table 1)
B. Blue/purple color material (refer to Table 2)
C. Alkali-soluble resin: cardo resin (chemical formula C-1)/Cardo resin (chemical formula C-2)/acrylic alkali soluble resin
D. Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kabushiki Kaisha)
E. Photopolymerization initiator: irgaqure-907 (manufactured by BASF corporation)
F. Solvent: propylene glycol monomethyl ether acetate
G. Thermal curing agent: alicyclic epoxy resin (chemical formula 3/chemical formula 4)/novolac epoxy resin (chemical formula 5)/silane-modified epoxy resin (chemical formula 6/chemical formula 7)
[ Table 5]
A. Scattering particles (see Table 1)
B. Blue/purple color material (refer to Table 2)
C. Alkali-soluble resin: cardo resin (chemical formula C-1)/Cardo resin (chemical formula C-2)/acrylic alkali soluble resin
D. Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kabushiki Kaisha)
E. Photopolymerization initiator: irgaqure-907 (manufactured by BASF corporation)
F. Solvent: propylene glycol monomethyl ether acetate
G. Thermal curing agent: alicyclic epoxy resin (chemical formula 3/chemical formula 4)/novolac epoxy resin (chemical formula 5)/silane-modified epoxy resin (chemical formula 6/chemical formula 7)
[ Table 6]
A. Scattering particles (see Table 1)
B. Blue/purple color material (refer to Table 2)
C. Alkali-soluble resin: cardo resin (chemical formula C-1)/Cardo resin (chemical formula C-2)/acrylic alkali soluble resin
D. Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kabushiki Kaisha)
E. Photopolymerization initiator: irgaqure-907 (manufactured by BASF corporation)
F. Solvent: propylene glycol monomethyl ether acetate
G. Thermal curing agent: alicyclic epoxy resin (chemical formula 3/chemical formula 4)/novolac epoxy resin (chemical formula 5)/silane-modified epoxy resin (chemical formula 6/chemical formula 7)
Manufacture of color filters
Color filters were produced using the metal oxide photosensitive resin compositions produced in the examples and comparative examples. That is, each of the photosensitive resin compositions was applied onto a glass substrate by a spin coating method, and then placed on a hot plate and maintained at a temperature of 100 ℃ for 3 minutes to form a thin film.
Next, a test photomask having a square transmission pattern with a width × height of 20mm × 20mm and a line/space pattern of 1 to 100 μm on the above-described film was irradiated with ultraviolet rays at a distance of 100 μm from the test photomask.
In this case, the ultraviolet light source was an ultra-high pressure mercury lamp manufactured by NIGHT MOTOR (trade name: USH-250D) and used at 200mJ/cm in the atmosphere2The exposure amount (365nm) of (A) was adjusted to the above range, and no special optical filter was used.
The film irradiated with ultraviolet light was immersed in a KOH aqueous solution developing solution having a ph of 10.5 for 80 seconds to be developed. After the glass plate coated with the film was washed with distilled water, it was dried by blowing nitrogen gas, and heated in a heating oven at 150 ℃ for 10 minutes to produce a color filter pattern. The film thickness of the color pattern produced above was 5.0. mu.m.
Experimental example 1: sensitivity and pattern stability of color filter
Sensitivity and pattern stability were measured for color filters produced from the photosensitive resin compositions of examples and comparative examples. The evaluation criteria for each experiment are as follows. The measurement results are shown in Table 7.
Sensitivity: degree of formation of thin film with no peeling of the fine pattern (1 to 60) of the sensitivity mask (lower numerical value, more excellent sensitivity)
Pattern stability: the degree of pattern error (error) of the pattern mask after exposure at low exposure (20-100 mJ)
O: pattern error free
And (delta): 1-2 pattern errors
X: pattern errors are more than 3
(. smallcircle.,. DELTA.,. times. are confirmation results by an optical microscope using a three-dimensional surface shape measuring apparatus)
Experimental example 2: solvent resistance and Heat resistance of color Filter
With respect to the color filters produced from the photosensitive resin compositions of the examples and comparative examples, whether or not the color filters exhibit stability in heat and solvents used in the production of color filters or in the production of liquid crystal display devices was evaluated by experiments for measuring heat resistance and solvent resistance. The measurement results are shown in Table 7.
Evaluation of solvent resistance: the color filters produced above were immersed in NMP (1-methyl-2-pyrrolidone) as a solvent for 30 minutes, and the color changes before and after the evaluation were calculated and compared for evaluation. In this case, the color change before and after evaluation was measured according to the following formula (1) representing the color change of the three-dimensional colorimeter defined by L, a, and b, and is shown in table 7 below.
Evaluation of heat resistance and change in luminance: the color filter prepared by the above method was heated in a heating furnace at 230 ℃ for two hours and then heated
The color change before and after the measurement was calculated by the following formula (1), and the results are shown in table 7 below.
Mathematical formula (1) Delta Eab*＝[(△L*)2+(△a*)2+(△b*)2]1/2
Δ Eab ≦ 1
△:△Eab＝1～3
x.DELTA.Eab > 3
Experimental example 3: experiment of degassing
For the measurement of the outgassing of the color filters manufactured from the photosensitive resin compositions of the examples and comparative examples, the blue photosensitive resin composition was coated on a glass substrate by a spin coating method, and then placed on a hot plate and maintained at a temperature of 100 ℃ for 3 minutes to form a thin film. Then, the film is coated on the substrateA mask (pattern region: 3X 3cm) was irradiated with ultraviolet light with a spacing of 100 μm from the test photomask. In this case, 100mJ/cm of 1kw high-pressure mercury or the like containing g, h, and i rays is used as the ultraviolet light source2The illumination of (2) is performed without using a special optical filter. The film irradiated with ultraviolet light was immersed in a KOH aqueous solution developing solution having a ph of 10.5 for two minutes to develop the film. After the glass plate coated with the film was washed with distilled water, it was dried by blowing nitrogen gas, and heated in a heating oven at 200 ℃ for 30 minutes.
The pattern shape (film) thickness of the color filter obtained by the method is 1 to 5 μm, and more preferably about 2 to 4 μm. The trapped compounds were analyzed by thermal decomposition of the thin film substrate formed as described above at 230 ℃ for 30 minutes using Py-GC/FID.
The analytical standards are as follows. The measurement results are shown in Table 7.
Degassing measurement: the values of comparative example 1 are expressed in percentage on a 100% basis. The lower the value, the more excellent the value.
Experimental example 4: fine pattern formation experiment
The pattern size of the color filter produced using the photosensitive resins of the examples and comparative examples was measured using an OM device (ECLIPSE LV100POL nicol) using a pattern size obtained by a line/space pattern mask designed to be 100 μm. The measurement results are shown in Table 6.
If the difference between the design value of the line/space pattern mask and the measured value of the obtained fine pattern is 20 μm or more, it is difficult to realize a fine pixel, and if it has a negative value, it means a critical value causing a process failure.
Example 5: determination of viewing angle
The Intensity (Intensity) of light generated at a viewing angle was measured using a variable angle photometer (GC-5000L, japan electrochrome) under a light transmission condition for a portion formed with a pattern of a 20 × 20mm square in a color filter produced using the photosensitive resin compositions produced in the above examples and comparative examples, and the diffusivity was calculated by the following equation 2. In the following mathematical formula 2, I represents light intensity measured from a viewing angle, I70、I20And I5Values measured at 70 degrees, 20 degrees and 5 degrees are indicated, respectively. Meaning that the higher the diffusivity, the more excellent the viewing angle. The measurement results are set forth in Table 7.
[ mathematical formula 2]
Diffusion rate ═ I70+I20)/2×I5×100
Experimental example 6: reflectance measurement
The light reflectance under light transmission conditions of the color filter produced using the photosensitive resin compositions produced in the examples and comparative examples was measured using a spectrocolorimeter CM-3600A (konica minolta corporation) at the portion formed with a pattern of a 20 × 20mm square, which means that the lower the measured reflectance, the more the external light reflection suppressing effect is improved, and the higher the quality of the high-quality picture is advantageous. The measurement results are shown in Table 7.
Example 7: measurement of luminescence intensity
In the color filters produced using the photosensitive resin compositions produced in the examples and comparative examples, the regions of the color filters formed with a pattern of 20 × 20mm squares were measured for light conversion using a 365nm Tube type 4W UV irradiator (VL-4LC, vilberroumat), and the examples and comparative examples were measured for emission intensity in the 450nm region using a spectrometer (Spectrum meter, ocean optics). The measurement results are shown in Table 7. Meaning that the higher the measured luminescence intensity, the higher the light efficiency.
[ Table 7]
In the case of examples 1 to 32 in which the Cardo-based binder resin and the thermal curing agent or the Cardo-based binder resin and the acrylic alkali-soluble resin were used together with the thermal curing agent, it was confirmed that excellent sensitivity, pattern stability and fine pattern were realized, and the reliability was more excellent because the heat resistance and the amount of outgas occurred were low. In contrast, in the case of comparative examples 1 to 8 in which the thermosetting agent was not included, it was confirmed that the sensitivity was lowered, the pattern stability and the fine pattern were difficult to be realized, the solvent resistance and the heat resistance were not good, and the reliability was lowered due to the excessive amount of outgas generation.
In addition, in the case of examples 1 to 32 including the configuration of the present invention, it was confirmed that the light emission intensity was all 20000 or more and the light efficiency was high. In contrast, in the case of comparative examples 1 to 8, it was confirmed that the light emission intensity was 13200 or less and the light efficiency was lowered, except in comparative example 1.
Further, in the case of examples 1 to 32 including the constitution of the present invention, it was confirmed that the reflectance was less than 4 and the external light reflection suppressing effect was improved and was advantageous for high quality picture quality. In contrast, in the case of comparative examples 1 to 4, it was confirmed that the reflectance was 10 or more and the external light reflection suppressing effect was significantly reduced.
In examples 1 to 32 including the configuration of the present application, it was confirmed that the diffusion rate was 30 or more and the viewing angle was excellent. In contrast, in the case of comparative examples 1 to 8, it was confirmed that the diffusion rate was 20 or less and the viewing angle was not good.
INDUSTRIAL APPLICABILITY
The present invention is excellent in heat resistance and does not cause yellowing at high temperatures and does not cause a change in emission intensity because of the inclusion of the blue photosensitive resin composition. Further, there is provided a color filter capable of improving display defects by minimizing the occurrence of outgassing and removing disconnection of electrodes formed between pixels, which is free and is caused by back-taper during a developing process, in a residual image that may occur when a panel is operated. Further, a self-luminous color filter of high quality image quality having an excellent viewing angle can be provided.
Claims (14)
1. A blue photosensitive resin composition comprising scattering particles, a blue colorant, a Cardo-based binder resin as a binder resin, a photoinitiator, a photopolymerizable compound, a thermal curing agent, and a solvent,
wherein the scattering particles comprise a metal oxide having an average particle diameter of 30 to 500nm,
wherein the Cardo-based binder resin is prepared by reacting one or more of the compounds represented by the following chemical formulas 1-1 and 1-2 with at least one of an acid anhydride and an acid dianhydride, wherein the thermal curing agent comprises one or more of a multifunctional alicyclic epoxy resin, a silane-modified epoxy resin, and a novolac-type epoxy resin,
[ chemical formula 1-1]
[ chemical formulas 1-2]
Wherein, in the chemical formula 1-1 or the chemical formula 1-2,
R1、R2、R3and R4Are each independently
X is hydroxyl;
R5is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
2. The blue photosensitive resin composition according to claim 1,
the scattering particles comprise a metal selected from the group consisting of Al2O3、SiO2、ZnO、ZrO2、BaTiO3、TiO2、Ta2O5、Ti3O5、Nb2O3SnO and MgO.
3. The blue photosensitive resin composition according to claim 1,
the blue colorant comprises one or more of a blue pigment and a blue dye.
4. The blue photosensitive resin composition according to claim 1,
the blue photosensitive resin composition further includes a violet colorant.
5. The blue photosensitive resin composition according to claim 1,
the blue photosensitive resin composition further includes an acrylic alkali-soluble resin as a binder resin.
6. The blue photosensitive resin composition according to claim 1,
the multifunctional alicyclic epoxy resin includes one or more compounds selected from the group consisting of compounds represented by the following chemical formula 3 and chemical formula 4,
[ chemical formula 3]
In the chemical formula 3, n, m and l are integers of 1 to 20,
[ chemical formula 4]
7. The blue photosensitive resin composition according to claim 1,
the phenolic epoxy resin includes a compound represented by the following chemical formula 5,
[ chemical formula 5]
In the chemical formula 5, o is an integer of 1 to 20.
8. The blue photosensitive resin composition according to claim 1,
the silane-modified epoxy resin is prepared by dealcoholization condensation reaction of a hydroxyl-containing epoxy resin and an alkoxysilane.
9. The blue photosensitive resin composition according to claim 8,
the hydroxyl group-containing epoxy resin is represented by the following chemical formula 6, the alkoxysilane is represented by the following chemical formula 7,
[ chemical formula 6]
In the chemical formula 6, q is an integer of 1 to 34,
[ chemical formula 7]
R6pSi(OR7)4-p
In chemical formula 7, p represents an integer of 0 or 1,
r6 represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms or an unsaturated aliphatic residue having 2 to 6 carbon atoms which may have a functional group directly bonded to a carbon atom,
r7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
each of the plurality of R7 may be the same or different.
10. The blue photosensitive resin composition according to claim 1,
the blue photosensitive resin comprises the following components in percentage by weight relative to the total weight of the blue photosensitive resin: 0.5 to 35 wt% of scattering particles; 0.5 to 40 weight percent of a blue colorant; 1.0 to 50 wt% of a binder resin; 0.5 to 15% by weight of a photopolymerizable compound; 0.2 to 15 weight percent of a photoinitiator; 0.1 to 20 wt% of a thermal curing agent; and 10 to 85 wt% of a solvent.
11. A color filter comprising a blue pattern layer composed of the blue photosensitive resin composition according to any one of claims 1 to 10.
12. The color filter according to claim 11,
the color filter further includes one or more selected from the group consisting of a red pattern layer and a green pattern layer.
13. The color filter according to claim 12,
the red pattern layer or the green pattern layer includes quantum dots.
14. An image display apparatus comprising:
a color filter according to claim 11; and
a light source emitting blue light.
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| PCT/KR2017/014135 WO2018182137A1 (en) | 2017-03-31 | 2017-12-05 | Blue photosensitive resin composition, and color filter and image display device manufactured using same |
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| CN1717628A (en) * | 2003-11-11 | 2006-01-04 | 三菱化学株式会社 | Curable composition, cured object, color filter, and liquid-crystal display |
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Also Published As
| Publication number | Publication date |
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| TW201837075A (en) | 2018-10-16 |
| WO2018182137A1 (en) | 2018-10-04 |
| KR102382059B1 (en) | 2022-04-04 |
| KR20180111493A (en) | 2018-10-11 |
| TWI666230B (en) | 2019-07-21 |
| CN110268328A (en) | 2019-09-20 |
| JP2020504843A (en) | 2020-02-13 |
| JP6921963B2 (en) | 2021-08-18 |
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