CN111694216B - Blue photosensitive resin composition for organic light emitting diode, color filter comprising same, and image display device - Google Patents
Blue photosensitive resin composition for organic light emitting diode, color filter comprising same, and image display device Download PDFInfo
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- CN111694216B CN111694216B CN202010172681.5A CN202010172681A CN111694216B CN 111694216 B CN111694216 B CN 111694216B CN 202010172681 A CN202010172681 A CN 202010172681A CN 111694216 B CN111694216 B CN 111694216B
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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
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
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- 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
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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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
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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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Abstract
The invention provides a blue photosensitive resin composition for an organic light emitting diode, a color filter and an image display device comprising the same, wherein the blue photosensitive resin composition for an organic light emitting diode comprises a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a sensitizer and a solvent, the colorant comprises a blue pigment and a xanthene dye, and the UV absorption wavelength of the sensitizer in the range of 300-400 nm has the maximum absorbance above 370nm, thereby providing the effect of reducing outgas (outgas) generated by decomposition of the colored photosensitive resin composition when manufacturing the color filter while improving the brightness, solvent resistance and moisture resistance of the colored photosensitive resin composition.
Description
Technical Field
The invention relates to a blue photosensitive resin composition for an organic light emitting diode, a color filter and an image display device including the same.
Background
With the formal entry into the information age, the field of displays that process and display a large amount of information has been rapidly developed, and accordingly, various flat panel displays have been developed and attracting attention.
Examples of such flat panel display devices include liquid crystal display devices (Liquid crystal display device: LCD), plasma display devices (Plasma Display Panel device: PDP), field emission display devices (Field Emission Display device: FED), electroluminescent display devices (Electroluminescence Display device: ELD), and organic light emitting display devices (Organic Light Emitting Diodes: OLED), and such flat panel display devices are used in various applications in the fields of home appliances such as televisions and video recorders, and in computers and mobile phones such as notebooks. In practice, these flat panel display devices are rapidly replacing the conventional Cathode Ray Tube (NIT) devices due to their excellent performances such as thickness reduction, light weight, and low power consumption.
In particular, OLEDs are rapidly applied to the market of small displays such as portable devices in recent years because the devices themselves emit light and can be driven at low voltages. In addition, not only a small-sized display but also a large-sized TV has been commercialized by mounting a color filter on a white OLED.
In addition, color filters are widely used in the above-mentioned flat panel displays and the like, and the application range thereof is rapidly expanding. Color filters used in color liquid crystal display devices, imaging elements, and the like are generally manufactured as follows: on a substrate on which a black matrix is patterned, a colored photosensitive resin composition containing pigments corresponding to each of red, green, and blue is uniformly applied by spin coating, and then a coating film formed by heat drying (hereinafter, also referred to as "pre-firing") is exposed to light and developed, and then further heat curing (hereinafter, also referred to as "post-firing") is performed as needed, and the above operation is repeated for each color, thereby forming pixels of each color.
However, when a conventional colored photosensitive resin composition is used to produce a color filter for an OLED, moisture is generated during the production process, the OLED having poor water resistance suffers from reduced color development and shortened lifetime, and there is a problem in that residual shadow is generated due to outgas (outgas) generated by decomposition of the colored photosensitive resin composition after high-temperature processing.
Korean laid-open patent No. 10-2003-0057307 discloses that a nanocomposite is used in order to block moisture, but when it is applied to a color filter for OLED, it is insufficient in terms of reliability such as brightness characteristics and solvent resistance.
Prior art literature
Patent literature
Patent document 1: korean laid-open patent No. 10-2003-0057307
Disclosure of Invention
Problems to be solved
In order to solve the above-described problems of the conventional techniques, an object of the present invention is to provide a colored photosensitive resin composition which is excellent in brightness, solvent resistance and moisture resistance and can reduce outgas (outgas) generated by decomposition of the colored photosensitive resin composition after high-temperature processing.
The present invention also provides a color filter produced using the colored photosensitive resin composition and an image display device including the color filter.
Means for solving the problems
In order to achieve the above object, the present invention provides a blue photosensitive resin composition for an organic light emitting diode, comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a sensitizer, and a solvent, wherein the colorant comprises a blue pigment and a xanthene dye, and the sensitizer has a maximum absorbance at 370nm or more at a UV absorption wavelength in the range of 300 to 400 nm.
The present invention also provides a color filter comprising a colored pattern produced from the above blue photosensitive resin composition.
Further, the present invention provides an image display device including the above color filter.
Effects of the invention
The blue photosensitive resin composition for an organic light emitting diode of the present invention provides an effect of reducing outgas (outgas) generated by decomposition of a colored photosensitive resin composition at the time of manufacturing a color filter while improving brightness, solvent resistance and moisture resistance of the colored photosensitive resin composition by containing a blue pigment and a xanthene dye as colorants and simultaneously using a sensitizer having maximum absorbance in a specific range.
Further, by using the blue photosensitive resin composition for an organic light emitting diode of the present invention, it is possible to manufacture a high-quality color filter and an image display device free from problems of reduced color development and reduced lifetime due to moisture and free from occurrence of residual shadows due to outgas.
Drawings
FIG. 1 is a graph showing the results of measuring UV absorption wavelength in the range of 300 to 400nm of a sensitizer used in an embodiment of the present invention.
Detailed Description
The present invention relates to a blue photosensitive resin composition for an organic light emitting diode, which contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a sensitizer and a solvent, wherein the colorant contains a blue pigment and a xanthene dye, and the sensitizer has a maximum absorbance at a UV absorption wavelength of 370nm or more in a range of 300 to 400nm, and a sensitizer having a maximum absorbance in a specific range is used as a colorant, so that it has been experimentally confirmed that outgas (outgas) generated by decomposition of the colored photosensitive resin composition when manufacturing a color filter can be reduced while improving the brightness, solvent resistance and moisture resistance of the colored resin composition.
Hereinafter, each component constituting the blue photosensitive resin composition of the present invention will be described in detail. However, the present invention is not limited to these components.
< blue photosensitive resin composition >
Coloring agent
The colorant is characterized by comprising a blue pigment and a xanthene dye.
The blue pigment may be contained in a proportion of 15:6, i.e. pigment blue, and the content of the blue pigment may be 30 to 98% by weight, preferably 50 to 92% by weight, based on the total weight of the solid components of the colorant. When the content of the blue pigment satisfies the above range, the brightness and color reproduction rate are high and the reliability is excellent, so that it is preferable.
The xanthene dye may be a compound represented by chemical formula 1.
[ chemical formula 1]
(in the above chemical formula 1, R 1 ～R 6 Each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a silyl group having 1 to 10 carbon atoms, or an organic acid group having 1 to 10 carbon atoms,
R 7 and R is 8 Each independently is hydrogen, -COOH, -COO - 、-SO 3- 、-SO 3 H、-SO 3 Na、-COOCH 3 or-COOCH 2 CH 3 。)
The compound represented by the above chemical formula 1 may be a commercially available xanthene dye, and preferably includes c.i. Acid Red 52 (Acid Red 52), c.i. Basic Red 1 (Basic Red 1), c.i. Basic Violet 10 (Basic Violet 10), c.i. Basic Violet 11 (Basic Violet 11), rhodamine B (Rhodamine B), rhodamine 6G (rhodomine 6G), rhodamine 123 (rhodomine 123), sulforhodamine B (Sulforhodamine B), and the like, but these xanthene dyes may be used alone or in combination of two or more.
The content of the xanthene dye is preferably 2 to 70% by weight, more preferably 8 to 50% by weight, and particularly preferably 10 to 60% by weight, based on the total weight of the solid content of the colorant. If the content of the xanthene dye in the colorant is within the above range, the problem of reduced reliability of dissolution of the dye due to the organic solvent after patterning can be prevented, and the sensitivity is excellent, so that it is preferable.
The above colorant may further comprise a dispersant. The dispersant is added to maintain the simultaneous deagglomeration and stability of the colorant, and any dispersant commonly used in the art can be used without limitation.
Examples of commercially available dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 112, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, lu Borun (Lubrizol) company's SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, and the like, but are not limited thereto.
These dispersants may be used alone or in combination of two or more, and it is preferable to use a dispersant having an acidic functional group, namely, disperbyk-2000, 2001 of the Pick company or SOLSPERSE-3000, 21000, 26000, 36600, 41000 of the Lubo company, but not limited thereto.
In the present invention, the content of the dispersant is not particularly limited, and the content of the dispersant may be 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the total solid content of the colorant contained at the same time. When the content of the dispersant is within the above range, a good viscosity can be obtained, and it is preferable from the viewpoints of micronization of the pigment and prevention of gelation after dispersion.
The content of the colorant may be 5 to 40% by weight, preferably 15 to 25% by weight, based on the total weight of the solid content of the blue curable resin composition for an organic light emitting diode. In the case where the above-mentioned colorant satisfies the above-mentioned content range, the color density of the pixel is sufficient, and the occurrence of residues can be prevented, so that it is preferable.
Alkali-soluble resin
The above alkali-soluble resin generally has reactivity and alkali-solubility based on the action of light or heat, and functions as a dispersion medium of a colorant. The alkali-soluble resin contained in the colored photosensitive resin composition of the present invention may function as a binder resin for a colorant, and is not particularly limited as long as the binder resin is soluble in an alkali developer used in a development stage for producing a color filter.
The alkali-soluble resin is not particularly limited, and may be a copolymer of a monomer having a carboxyl group and another monomer copolymerizable therewith.
Examples of the monomer having a carboxyl group include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule, and the like.
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, and cinnamic acid.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like.
The unsaturated polycarboxylic acid may be an acid anhydride, and specifically maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polycarboxylic acid may be a mono (2-methacryloxyalkyl) ester thereof, and examples thereof include succinic acid mono (2-acryloxyethyl) ester, succinic acid mono (2-methacryloxyethyl) ester, phthalic acid mono (2-acryloxyethyl) ester, phthalic acid mono (2-methacryloxyethyl) ester, and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends thereof, and examples thereof include ω -carboxyl polycaprolactone monoacrylate and ω -carboxyl polycaprolactone monomethacrylate. These carboxyl group-containing monomers may be used either individually or in combination of two or more.
Examples of the other monomer copolymerizable with the monomer having a carboxyl group 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 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, methoxydiglycol acrylate, methoxydiglycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, unsaturated carboxylic acid esters such as dicyclopentadiene acrylate, dicyclopentadiene methacrylate, dicyclopentadienyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate;
Unsaturated carboxylic acid aminoalkyl esters such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate;
glycidyl esters of unsaturated carboxylic acids 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, vinylidene cyanide and the like;
unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylamide, and the like;
unsaturated imides such as maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; and
polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and a macromonomer having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer chain of the polysiloxane. These monomers may be used each alone or in combination of two or more.
In particular, the other monomer copolymerizable with the monomer having a carboxyl group is more preferable because a bulky monomer such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, or a monomer having a rosin skeleton tends to lower the relative permittivity value.
The alkali-soluble resin may have a molecular weight distribution, that is, a weight average molecular weight ratio, of 1.5 to 6.0, preferably 1.8 to 4.0, and in this case, there is an advantage that the developability can be improved.
The acid value of the alkali-soluble resin may be 20 to 200mgKOH/g, preferably 50 to 150mgKOH/g, based on the solid content. If the acid value of the alkali-soluble resin is in the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved, and the sensitivity is increased, and as a result, the pattern of the exposed portion is left at the time of development, and the film retention rate (film remaining ratio) can be improved, which is preferable.
In the present invention, 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 measured by titration using an aqueous potassium hydroxide solution.
The weight average molecular weight (hereinafter, abbreviated as "weight average molecular weight") of the alkali-soluble resin in terms of polystyrene as measured by gel permeation chromatography (GPC, tetrahydrofuran as an eluting solvent) may be 3,000 ～ 200,000, and more preferably 5,000 ～ 100,000. When the weight average molecular weight is within the above range, the hardness of the coating film is increased, the film retention rate is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution can be improved.
The content of the alkali-soluble resin may be 5 to 85% by weight, and preferably 10 to 70% by weight, based on the total weight of the solid content of the blue photosensitive resin composition for an organic light emitting diode. When the content of the alkali-soluble resin satisfies the above range, the solubility in the developer is sufficient, and the non-pixel portion is less likely to cause development residues on the substrate, and the film of the pixel portion of the exposure portion is prevented from decreasing during development, and the non-pixel portion is preferably peeled off.
Photopolymerizable compound
The photopolymerizable compound is a compound that can be polymerized by irradiation with light by means of active radicals, acids, and the like generated by the photopolymerization initiator, and is not particularly limited as long as it can be polymerized by the action of the photopolymerization initiator. Preferably, a monofunctional monomer, a difunctional monomer, a trifunctional or more polyfunctional monomer, or the like may be used, and one or more monomers selected from them may be used.
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, and examples of the commercially available products include ARONIX M-101 (east Asian Synthesis), KAYARAD TC-110S (Japan chemical Co., ltd.), and VISCOAT 158 (Osaka organic chemical industry), but are not limited thereto.
Specific examples of the difunctional monomers include 1, 4-butanediol di (meth) acrylate, 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, and examples of the commercially available products include ARONIX M-210, M-1100, M-1200 (Toyama Co., ltd.), KAYARAD HDDA (Japan chemical Co., ltd.), VISCOAT 260 (Osaka organic chemical industry), AH-600, AT-600, UA-306H (co-Rong chemical Co., ltd.).
Specific examples of the above-mentioned trifunctional or higher polyfunctional photopolymerizable compounds include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and the like, and examples of the commercial products include aromix M-309, TO-1382 (east asia synthesis), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPHA-40H (japan chemical).
Among the photopolymerizable compounds exemplified above, a polyfunctional monomer having a difunctional or higher functionality is preferably used, and from the viewpoint of having excellent polymerizability and being capable of improving strength, (meth) acrylates and urethane (meth) acrylates are more preferably used.
The content of the photopolymerizable compound may be 5 to 50% by weight, and preferably 7 to 45% by weight, based on the total weight of the solid content of the blue photosensitive resin composition for an organic light emitting diode. When the content of the photopolymerizable compound satisfies the above range, the strength or smoothness of the pixel (pixel) portion may be improved, which is preferable.
Photopolymerization initiator
The photopolymerization initiator is a compound that generates radicals or the like capable of initiating polymerization of the photopolymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like.
The photopolymerization initiator may be characterized by containing an oxime compound, and preferably may be characterized by containing one or more selected from the group consisting of a compound represented by the following chemical formula 2, a compound represented by the following chemical formula 3, and a compound represented by the following chemical formula 4.
(R in the above chemical formulas 2 to 4) 11 ～R 26 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 12 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 24 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an aralkyl group, an amino group, a nitro group, a cyano group or a hydroxyl group. )
The content of the oxime compound is not particularly limited as long as it is within a range capable of fully exerting its function, and the content thereof may be preferably 5 to 100% by weight based on 100% by weight of the entire photopolymerization initiator. When the content of the oxime compound is within the above range, brightness and sensitivity can be further improved, which is preferable.
The photopolymerization initiator may further include other photopolymerization initiators without any particular limitation as long as the photopolymerization initiator can polymerize the binder resin and the photopolymerizable compound within a range that does not impair the object of the present invention.
Typical examples of the other photopolymerization initiator include acetophenone compounds, benzoin compounds, benzophenone compounds, bisimidazole compounds, triazine compounds, thioxanthone compounds, anthracene compounds, and the like, but the present invention is not limited thereto, and one or more of them may be further contained and used.
Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzildimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and more preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one.
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
Examples of the benzophenone compound include benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3', 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone.
Examples of the bisimidazole compound include 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4', 5' -tetraphenylbisimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetrakis (trialkoxyphenyl) biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -biimidazole, or imidazole compounds wherein the phenyl group at the 4,4', 5' position is substituted with an alkoxycarbonylyl group, and the like. Of these, more preferable examples include 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenyl bisimidazole or 2, 2-bis (2, 6-dichlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -bisimidazole, and the like.
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-piperonyl-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) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethylene ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) ethylene ] -1,3, 5-triazine.
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
Examples of the anthracene compound include 9, 10-dimethoxy anthracene, 2-ethyl-9, 10-dimethoxy anthracene, 9, 10-diethoxy anthracene, and 2-ethyl-9, 10-diethoxy anthracene.
As other specific examples, there may be mentioned 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9, 10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like.
The content of the photopolymerization initiator may be 0.1 to 20% by weight, and preferably 0.5 to 10% by weight, based on the total weight of the solid content of the blue photosensitive resin composition for an organic light emitting diode. When the content of the photopolymerization initiator is within the above range, the photosensitive resin composition is highly sensitive and the exposure time is shortened, so that productivity can be improved and high resolution can be maintained. Further, the strength of a pixel portion formed using the blue photosensitive resin composition for an organic light emitting diode of the present invention and the smoothness of the surface of the pixel portion may be improved.
Sensitizer
The sensitizer can reduce the activation energy (activation energy) of the photopolymerization initiator. In particular, in the case of using a sensitizer having a UV absorption wavelength of 300 to 400nm and a maximum absorbance of 370nm or more, the light absorption rate can be improved while avoiding the wavelength at which the photopolymerization initiator is activated, and thus the efficiency of photopolymerization reaction can be further improved, whereby the content of the photopolymerization initiator can be reduced and the Outgas (Outgas) generation of the above-mentioned photopolymerizable composition can be reduced.
The sensitizer may be used without limitation as long as it has a maximum absorbance at a UV absorption wavelength of 370nm or more between 300 and 400nm, and preferably may contain one or more selected from the group consisting of benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, xanthene compounds and tertiary amine compounds.
Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Specific examples of the acetophenone compound include acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, and 1, 1-dichloroacetophenone.
Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
Specific examples of the thioxanthone compound include 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, and 2, 4-diisopropylthioxanthone.
Specific examples of the ketal compound include acetophenone dimethyl ketal and benzil dimethyl ketal.
Specific examples of the benzophenone compound include benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4 ' -methyl diphenyl sulfide, 4-benzoyl-4 ' -ethyl diphenyl sulfide, and 4-benzoyl-4 ' -propyl diphenyl sulfide.
The tertiary amine compound is specifically a coumarin compound containing a dialkylamino group such as an ethanolamine compound or a compound having a dialkylaminobenzene structure, for example, a dialkylaminobenzophenone such as 4,4 '-dimethylaminobenzophenone (NISSOCURE MABP manufactured by soyama corporation), 4' -diethylaminobenzophenone (EAB manufactured by baogu chemical corporation), a dialkylamino-containing coumarin compound such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), 4-dimethylaminoethyl benzoate (KAYACURE EPA manufactured by kayama chemical corporation), ethyl 2-dimethylaminobenzoate (quantation DMB manufactured by international bio-synthesis corporation), 4-dimethylaminobenzoate (n-butoxyethyl 4) (anta manufactured by international bio-synthesis corporation), isopentyl ethyl p-dimethylaminobenzoate (kadmbi manufactured by kakuol chemical corporation), 4-dimethylaminobenzoate (2-ethyl benzoate) (VAN manufactured by dak chemical corporation), or the like.
The sensitizer may be contained in an amount of 10 to 30 parts by weight, preferably 10 to 15 parts by weight, based on 100 parts by weight of the photopolymerization initiator. In the case where the content of the sensitizer satisfies the above range, good photosensitization margin (photomargin) and solubility can be obtained, and thus, it is preferable.
Solvent(s)
The solvent is not particularly limited as long as it is effective in dissolving other components contained in the photosensitive resin composition, and solvents generally used in the art can be used. Specific examples of the solvent include, but are not limited to, one or more selected from ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like.
Specific examples of the ether solvent 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; etc.
Specific examples of the above-mentioned acetate solvents include alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate;
Alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; etc.
Specific examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.
Specific examples of the ketone solvent include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.
Specific examples of the alcohol solvent include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and the like.
Specific examples of the ester solvent include cyclic esters such as gamma-butyrolactone; ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and the like.
Specific examples of the amide-based solvent include N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and the like.
From the viewpoint of coatability and drying properties, the solvent may be an organic solvent having a boiling point of 100 to 200 ℃, and alkylene glycol alkyl ether acetates are preferably used; ketones; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used. These solvents may be used each alone or in combination of two or more.
The content of the solvent may be 60 to 90 wt%, and preferably may be 70 to 85 wt%, with respect to the total weight of the blue photosensitive resin composition for an organic light emitting diode. When the content of the solvent is within the above range, the coatability can be improved when coating is performed by a coating apparatus such as a roll coater, a spin coater, a slot coater (sometimes referred to as a die coater), or an inkjet printer.
Additive agent
The blue photosensitive resin composition for an organic light emitting diode of the present invention may further contain additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, and anticoagulants, as required by those skilled in the art, in addition to the above-mentioned components, within a range that does not impair the object of the present invention.
Specific examples of the filler include, but are not limited to, glass, silica, alumina, and the like.
Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, and the like, but are not limited thereto.
Specific examples of the adhesion promoter include at least one selected from vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanatopropyl trimethoxysilane and 3-isocyanatopropyl triethoxysilane.
Specific examples of the antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3, 5-di-t-pentylphenyl) ethyl ] -4, 6-di-t-pentylphenyl acrylate, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2,4,8, 10-tetra-t-butyldibenzo [ d, f ] [1,3,2] dioxaphosphepin, 3, 9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy } -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane, 2' -methylenebis (6-tert-butyl-4-methylphenol), 4' -methylenebis (6-tert-butyl-3-methylphenol), 4' -thiobis (2-tert-butyl-5-methylphenol), 2' -thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3' -thiodipropionate, dimyristyl 3,3' -thiodipropionate distearyl 3,3' -thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 3',3", 5',5" -hexa-tert-butyl-a, a ', a "- (mesitylene-2, 4, 6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2, 6-di-tert-butyl-4-methylphenol, 2' -thiobis (4-methyl-6-tert-butylphenol), 2, 6-di-tert-butyl-4-methylphenol, and the like, but are not limited thereto.
Specific examples of the ultraviolet absorber include, but are not limited to, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.
Specific examples of the coagulant inhibitor include sodium polyacrylate, but are not limited thereto.
The method for producing the blue photosensitive resin composition for an organic light emitting diode of the present invention can be described by using a method generally used in the art without limitation, and is specifically described below.
First, the pigment in the colorant is mixed with a solvent, and dispersed by a bead mill or the like until the average particle diameter of the pigment becomes 0.2 μm or less. In this case, if necessary, a pigment dispersant, a part or all of the alkali-soluble resin, or a dye may be mixed with a solvent to be dissolved or dispersed.
The blue photosensitive resin composition for an organic light emitting diode of the present invention can be produced by further adding a dye, the remaining alkali-soluble resin, the photopolymerizable compound, the photopolymerization initiator and sensitizer, and if necessary, the additive and solvent to the above-described mixed dispersion so as to have a predetermined concentration.
< color Filter >
An aspect of the present invention relates to a high-quality color filter which is produced using the blue photosensitive resin composition for an organic light emitting diode, and which is free from problems of reduced color development and reduced lifetime due to moisture and free from residual shadows due to outgas.
The color filter includes a substrate and a pattern layer formed on an upper portion of the substrate.
The substrate may be the color filter itself substrate, or may be a portion of a display device or the like where a color filter is located, 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 pattern layer may be a layer containing the colored photosensitive resin composition of the present invention, which is formed by applying the colored photosensitive resin composition, and then exposing the applied layer to light in a predetermined pattern, developing the applied layer, and thermally curing the applied layer. The pattern layer may be formed by performing a method generally known in the art.
The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between the patterns, and may further include a black matrix, but is not limited thereto.
Further, the color filter may further include a protective film formed on an upper portion of the pattern layer of the color filter.
< image display device >
Further, another embodiment of the present invention relates to a high-quality image display device in which the color development is reduced and the lifetime is reduced due to moisture and in which residual shadows due to outgas are not generated by including the color filter.
The image display device of the present invention includes the color filter, and specific examples thereof include liquid crystal displays, OLEDs, flexible displays, and the like, but are not limited thereto.
In the following, preferred embodiments are provided for the purpose of facilitating understanding of the present invention, but it will be apparent to those skilled in the art that the following embodiments are merely illustrative, and various changes and modifications can be made within the scope and technical spirit of the present invention, and of course such changes and modifications are also within the scope of the appended claims. In the following examples and comparative examples, "%" and "parts" representing contents are weight basis unless otherwise specified.
<Examples>
Synthesis example 1: synthesis of photopolymerization initiator D-3
Synthesis of reactant 1
Fluorene 200.0g, potassium hydroxide 268.8g and potassium iodide 19.9g were dissolved in anhydrous dimethyl sulfoxide 1L under nitrogen atmosphere, and after maintaining the reaction at 15 ℃, bromoethane 283.3g was slowly added over 2 hours, and the reaction was stirred at 15 ℃ for 1 hour. Then, distilled water 2L was added to the reaction mass, after stirring for 30 minutes, the resultant was extracted with dichloromethane 2L, the extracted organic layer was washed 2 times with distilled water 2L, then the recovered organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure, whereby the resultant was fractionated under reduced pressure, whereby 248.6g of pale yellow reaction mass 1 (9, 9-diethyl-9H-fluorene) was obtained as a liquid having a high viscosity.
Synthesis of reactant 2
100.5g of the above-mentioned reactant 1 was dissolved in 1L of methylene chloride, cooled to-5℃and then 72.3g of aluminum chloride was slowly added thereto, and 50.1g of propionyl chloride diluted in 50ml of methylene chloride was slowly added thereto over 2 hours while preventing the temperature of the reactant from rising, and the reactant was stirred at-5℃for 1 hour. Then, the reaction product was slowly poured into ice water 1L, stirred for 30 minutes, and after separating the organic layer, the organic layer was washed with 500ml of distilled water, the recovered organic layer was distilled under reduced pressure, and the resultant was purified by silica gel column chromatography (developing solvent; ethyl acetate: n-hexane=1:4), whereby 75.8g of reactant 2 (1- (9, 9-diethyl-9H-fluoren-2-yl) -1-propanone) was obtained as a pale yellow solid.
Synthesis of reactant 3
44.5g of reactant 2 were dissolved in 900ml of Tetrahydrofuran (THF), and the solution in 1, 4-di-were added successivelyAlkane 4N HCl 150ml and isobutyl nitrite 24.7g, the reaction was stirred at 25℃for 6 hours. Then, 500ml of ethyl acetate was added to the reaction solution, the organic layer was separated by stirring for 30 minutes, then washed with 600ml of distilled water, then the recovered organic layer was dried with anhydrous magnesium sulfate, the solvent was distilled under reduced pressure, and the thus obtained solid product was recrystallized using 300ml of a mixed solvent of ethyl acetate: hexane (1:6) and dried, whereby 27.5g of reactant 3 (1- (9, 9-diethyl-9H-fluoren-2-yl) -1, 2-propanedione-2-oxime) was obtained as a pale gray solid.
Synthesis of photopolymerization initiator D-3
Reactant 3 was dissolved in N-methyl-2-pyrrolidone (NMP) 1L under a nitrogen atmosphere, and after maintaining the temperature of the reactant at-5 ℃, 35.4g of triethylamine was added, and after stirring the reaction solution for 30 minutes, a solution in which 27.5g of acetyl chloride was dissolved in 75ml of N-methyl-2-pyrrolidone was slowly added over 30 minutes, and stirring was performed for 30 minutes while preventing the temperature of the reactant from rising. Then, distilled water 1L was slowly added to the reaction mixture, and after the organic layer was separated by stirring for 30 minutes, the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained solid product was recrystallized from 1L of ethanol and dried, whereby 93.7g of a photopolymerization initiator D-3 (1- (9, 9-diethyl-9H-fluoren-2-yl) -1, 2-propanedione-2-oxime-O-acetate) which is a compound represented by chemical formula 4 as a light gray solid was obtained.
Synthesis example 2: synthesis of alkali-soluble resin
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared, and on the other hand, 74.8g (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 charged as a monomer drop funnel, and then stirred and mixed to prepare a chain transfer agent drop tank, and 6g of n-dodecylmercaptan and 24g of PGMEA were charged and stirred and mixed to prepare a flask. Thereafter, 395g of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen gas from air, and the temperature of the flask was raised to 90 ℃ with stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. At the time of the dropwise addition, the temperature was maintained at 90℃for 2 hours, 1 hour later, the temperature was raised to 110℃and maintained for 3 hours later, and then a gas introduction tube was introduced to start bubbling of an oxygen/nitrogen=5/95 (v/v) mixed gas. Then, 28.4g [ (0.10 mol), (33 mol% relative to the carboxyl group of acrylic acid used in the present reaction) ] of glycidyl methacrylate, 0.4g of 2,2' -methylenebis (4-methyl-6-t-butylphenol), and 0.8g of triethylamine were charged into a flask, and the reaction was continued at 110℃for 8 hours to obtain an alkali-soluble resin having a solid content acid value of 70 mg KOH/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.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin were measured by GPC under the following conditions, and the ratio of the weight average molecular weight to the number average molecular weight obtained below was defined as the molecular weight distribution (Mw/Mn).
-means for: HLC-8120GPC (manufactured by Tosoh Co., ltd.)
-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 μl
-a detector: RI (RI)
-determining the sample concentration: 0.6 mass% (solvent = tetrahydrofuran)
Calibration standard: TSK standard polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corp.)
Manufacturing example: production of colored Dispersion
Production example 1: coloring ofDispersion M-1
10.12 parts by weight of C.I. pigment blue 15:6, 3.88 parts by weight of C.I. acid red 52, 4.84 parts by weight of an acrylic dispersant (Disperbyk-2000, manufactured by Pick corporation), 3.88 parts by weight of the resin of Synthesis example 2, 68.04 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 9.24 parts by weight of propylene glycol monomethyl ether, and 360 parts by weight of 0.2mm diameter zirconium dioxide beads were put into a mayonnaise bottle having a capacity of 140ml, and kneaded at 60℃for 10 hours by a paint conditioner to perform a dispersion treatment. Thereafter, the zirconium dioxide beads were removed to obtain a dispersion. The above dispersion was filtered through a membrane filter having a pore size (pore size) of 1.0. Mu.m, to thereby produce a colored dispersion M-1.
Production example 2: coloring dispersion M-2
A coloring dispersion M-2 was produced in the same manner as in production example 1, except that c.i. basic red 1 was used instead of c.i. acid red 52 used in production example 1.
Production example 3: coloring dispersion M-3
A coloring dispersion M-3 was produced in the same manner as in production example 1, except that rhodamine 6G was used instead of c.i. acid red 52 used in production example 1.
Production example 4: coloring dispersion M-4
A coloring dispersion M-4 was produced in the same manner as in production example 1, except that c.i. pigment violet 23 was used instead of c.i. acid red 52 used in production example 1.
Examples 1 to 9 and comparative examples 1 to 5
Blue photosensitive resin compositions for organic light emitting diodes of examples 1 to 9 and comparative examples 1 to 5 were produced according to the compositions of table 1 below.
TABLE 1
(unit: wt%)
-a colouring dispersion M-1: coloring Dispersion liquid of production example 1
-a colouring dispersion M-2: coloring dispersion liquid of production example 2
-a colouring dispersion M-3: coloring dispersion liquid of production example 3
-a colouring dispersion M-4: coloring dispersion liquid of production example 4
Alkali-soluble resin B: synthesis example 2 alkali-soluble resin
Photopolymerisable compound C: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Japanese chemical Co., ltd.)
Photopolymerization initiator D-1: OXE-01 (Basf Co.)
Photopolymerization initiator D-2: OXE-02 (Basf Co.)
Photopolymerization initiator D-3: synthesis example 1 photopolymerization initiator
Sensitizer E-1: 2.4-Diethylthioxanthone (2.4-Diethyl thioxanthone, cambridge Co.),. Lambda.max: 385nm
Sensitizer E-2: TR-PSS-303 (Tronly Co.),. Lambda.max: 380nm
Sensitizer E-3: TR-PSS-202 (Tronly Co.), λmax:400nm
Sensitizer E-4: TR-PAD-103 (Tronly Co.), λmax:355nm
Sensitizer E-5:4, 4'-bis (diethylamino) benzophenone (4, 4' -Bis (diethylamino) benzophenone, delphinium chemical Co., ltd.). Lambda.max: 355nm
Additive F: SH-8400 (daokanning)
-solvent G: propylene Glycol Monomethyl Ether Acetate (PGMEA)
Manufacturing example: color filter fabrication
The blue photosensitive resin compositions of examples 1 to 9 and comparative examples 1 to 5 were applied to a glass substrate of 5X 5cm and dried, and then bar-coated so that the thickness became 2.5. Mu.m. Then, after drying in an oven at 100℃for 3 minutes to remove the solvent, the film was exposed to light at a distance of 300 μm from the photomask so that the cumulative light amount at 313nm wavelength of the FUSION lamp became 40mJ, immersed in KOH aqueous solution at pH 14 for 3 minutes, taken out, immersed again in distilled water for 1 minute, taken out, and cured in an oven at 230℃for 20 minutes to produce a color filter.
< Experimental example >
Experimental example 1 measurement of brightness
The color filter produced as described above was set in a spectrophotometer (CM-3700 d, product of konikama-midada sensor, inc.) to measure the transmitted chromaticity of X, Y, Z coordinate axis at 2 ° of the C light source, and the Y value at this time was taken as luminance. The results are shown in Table 2 below.
The luminance values shown in table 2 below are expressed as relative values when the luminance of the color filter manufactured using the blue photosensitive resin composition of comparative example 1 is set to a standard (100%).
Experimental example 2 evaluation of Heat resistance
The color filters produced above were each cut at 3X 3cm and immersed in 14.6ml of NMP (N-Methyl-2-pyrrolidone) solution at 80℃for 40 minutes. Then, absorbance was measured by an ultraviolet-visible spectrophotometer (UV-Vis spectrometer), and the results were evaluated according to the following evaluation criteria, and are shown in table 2 below.
< Heat resistance evaluation criterion >
O: the absorbance is 1 or less
Delta: absorbance of more than 1 and less than 3
X: absorbance of greater than 3
Experimental example 3 analysis of outgassing
The gas composition of the sublimated substance generated while the color filter manufactured above was heated at 230 degrees for 30 minutes by GC/MS was analyzed. Analysis of sublimation components (outgas) of the coating film formed with the remaining composition was performed by comparing the total amount of the compound components detected from the gas components generated by the coating film manufactured with the blue photosensitive resin composition of comparative example 3 described above with 100% as a reference.
The analysis results are shown in table 2 below, and the smaller the total amount, the more excellent the material.
Experimental example 4 measurement of moisture adsorption amount
After the color filter manufactured above was left to stand in a hygrostat maintained at 80% humidity for 30 minutes, the content of moisture generated during 30 minutes was measured at 150 ℃ using TDS1200 (ESCO).
The above measurement results are shown in table 2 below, and smaller measurement values mean smaller moisture contents.
TABLE 2
| Differentiation of | Brightness (%) | Evaluation of solvent resistance | Outgassing analysis | Moisture adsorption quantity (ppm) |
| Example 1 | 108％ | ○ | 50％ | 0.35 |
| Example 2 | 109％ | ○ | 55％ | 0.31 |
| Example 3 | 108％ | ○ | 52％ | 0.38 |
| Example 4 | 112％ | ○ | 72％ | 0.48 |
| Example 5 | 111％ | ○ | 76％ | 0.47 |
| Example 6 | 113％ | ○ | 73％ | 0.45 |
| Example 7 | 108％ | ○ | 76％ | 0.40 |
| Example 8 | 109％ | ○ | 74％ | 0.42 |
| Example 9 | 108％ | ○ | 78％ | 0.39 |
| Comparative example 1 | 100％ | ○ | 63％ | 0.39 |
| Comparative example 2 | 97％ | Δ | 90％ | 0.51 |
| Comparative example 3 | 104％ | X | 100％ | 0.89 |
| Comparative example 4 | 107％ | X | 130％ | 0.97 |
| Comparative example 5 | 102％ | X | 136％ | 0.88 |
Referring to the results of table 2 above, in the case of examples 1 to 9 of the present application containing a blue pigment and a xanthene-based dye as colorants and containing a sensitizer having a UV absorption wavelength in the range of 300 to 400nm and having a maximum absorbance at 370nm or more, it was confirmed that excellent effects were exhibited in terms of brightness, solvent resistance, outgas characteristics, and moisture resistance.
In contrast, in the case of comparative examples 1 and 2 containing no xanthene dye, it was confirmed that the luminance and outgas characteristics were reduced, and in the case of comparative examples 3 to 5 using a sensitizer having a UV absorption wavelength in the range of 300 to 400nm and having the maximum absorbance at less than 370nm, it was confirmed that the solvent resistance, outgas characteristics and moisture resistance were significantly reduced.
Accordingly, it is understood that the blue photosensitive resin composition for an organic light emitting diode of the present invention contains a blue pigment and a xanthene dye as colorants, and contains a sensitizer having a maximum absorbance at a UV absorption wavelength of 370nm or more in a range of 300 to 400nm, thereby improving the brightness, solvent resistance and moisture resistance of the colored photosensitive resin composition and reducing outgas (outgas) generated by decomposition of the colored photosensitive resin composition when manufacturing a color filter.
Claims (10)
1. A blue photosensitive resin composition for an organic light emitting diode, comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a sensitizer and a solvent,
comprises 5 to 40% by weight of a colorant, 5 to 85% by weight of an alkali-soluble resin, 5 to 50% by weight of a photopolymerizable compound and 0.1 to 20% by weight of a photopolymerization initiator, based on the total weight of the solid content of the blue photosensitive resin composition for an organic light emitting diode,
comprising 60 to 90 wt% of a solvent based on the total weight of the blue photosensitive resin composition for an organic light emitting diode,
the colorant comprises a blue pigment and a xanthene dye,
the sensitizer has a maximum absorbance at a wavelength of UV absorption of 370nm or more in a range of 300 to 400 nm.
2. The blue photosensitive resin composition for an organic light emitting diode according to claim 1, wherein the blue pigment is c.i. pigment blue 15:6.
3. The blue photosensitive resin composition for an organic light emitting diode according to claim 1, wherein the xanthene dye is a compound represented by the following chemical formula 1,
chemical formula 1
In the chemical formula 1, R 1 ～R 6 Each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a silyl group having 1 to 10 carbon atoms, or an organic acid group having 1 to 10 carbon atoms,
R 7 and R is 8 Each independently is hydrogen, -COOH, -COO - 、-SO 3- 、-SO 3 H、-SO 3 Na、-COOCH 3 or-COOCH 2 CH 3 。
4. The blue photosensitive resin composition for an organic light emitting diode according to claim 1, wherein the sensitizer is one or more selected from the group consisting of benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, xanthene compounds, and tertiary amine compounds.
5. The blue photosensitive resin composition for an organic light emitting diode according to claim 1, wherein the photopolymerization initiator comprises an oxime compound.
6. The blue photosensitive resin composition for an organic light emitting diode according to claim 1, wherein the photopolymerization initiator comprises at least one selected from the group consisting of a compound represented by the following chemical formula 2, a compound represented by the following chemical formula 3, and a compound represented by the following chemical formula 4,
chemical formula 2
Chemical formula 3
Chemical formula 4
In the chemical formulas 2 to 4, R 11 ～R 26 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 12 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 24 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an aralkyl group, an amino group, a nitro group, a cyano group or a hydroxyl group.
7. The blue photosensitive resin composition for an organic light emitting diode according to claim 1, wherein the photopolymerizable compound is one or more selected from the group consisting of nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, 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, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
8. The blue photosensitive resin composition for an organic light emitting diode according to claim 1, further comprising one or more additives selected from the group consisting of a filler, other polymer compound, adhesion promoter, antioxidant, ultraviolet absorber and anti-coagulant.
9. A color filter comprising a colored pattern produced from the colored photosensitive resin composition for an organic light emitting diode according to any one of claims 1 to 8.
10. An image display device comprising the color filter of claim 9.
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| KR1020190028174A KR102558491B1 (en) | 2019-03-12 | 2019-03-12 | A blue color photosensitive resin composition for organic light emitting diodes, a color filter and an image display device comprising the same |
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