CN108375875B - Colored photosensitive resin composition, color filter and image display device - Google Patents

Colored photosensitive resin composition, color filter and image display device Download PDF

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CN108375875B
CN108375875B CN201810046204.7A CN201810046204A CN108375875B CN 108375875 B CN108375875 B CN 108375875B CN 201810046204 A CN201810046204 A CN 201810046204A CN 108375875 B CN108375875 B CN 108375875B
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resin composition
photosensitive resin
colored photosensitive
compound
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CN108375875A (en
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柳在范
金韩善
尹钟元
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Dongwoo Fine Chem Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • 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
    • 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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  • Physics & Mathematics (AREA)
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  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
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Abstract

The present invention relates to a colored photosensitive resin composition, a color filter and an image display device manufactured by using the same, wherein the colored photosensitive resin composition is characterized by comprising: a photopolymerizable compound which contains one or more moieties (moieity) selected from the group consisting of ethylene oxide and propylene oxide in a molecular structure and is trifunctional or higher than a urethane acrylic or a structural analogue thereof; a colorant containing a rhodamine-based dye in a particle form; and a dispersant containing a triazine compound.

Description

Colored photosensitive resin composition, color filter and image display device
Technical Field
The present invention relates to a colored photosensitive resin composition, a color filter and an image display device manufactured by using the same.
Background
Color filters are widely used in various display devices such as image sensors and Liquid Crystal Displays (LCDs), and their application range is rapidly expanding. The color filter is formed of 3 color patterns of Red (Red), Green (Green), and Blue (Blue), or 3 color patterns of Yellow (Yellow), Magenta (Magenta), and Cyan (Cyan).
The above color filters widely used for display devices are generally manufactured as follows: a color filter is manufactured by uniformly applying a colored photosensitive resin composition containing a pigment dispersion composition corresponding to the color of each pattern on a substrate on which a black matrix pattern is formed by spin coating or slit coating, then drying by heating, exposing and developing the formed coating film, and further curing by heating as necessary, and repeating the above operation for each color to form pixels of each color.
A color filter using the colored photosensitive resin composition described above is required to have physical properties such as high brightness and high contrast, and pixels having high color reproducibility have been recently required. Therefore, the content of the pigment and the carbon black of the coloring material used in the above colored resin composition gradually increases. However, when the content of the coloring material in the colored resin composition is increased, the pigment must be finely pulverized in order to exhibit excellent optical characteristics, and particularly, when a high-concentration pigment-dispersed composition is produced, the viscosity becomes high, or the storage stability of the pigment-dispersed composition such as gelation during storage is deteriorated, and thus there is a problem that the optical characteristics such as brightness and contrast are deteriorated.
Japanese laid-open patent publication No. 2013-61619 relates to a blue colorant composition for color filters and a color filter substrate using the same, and discloses the following: the blue colorant composition for color filters is characterized by comprising at least a colorant, a binder resin, a polymeric dispersant and a solvent, wherein the colorant comprises a pigment and a rhodamine dye, and the rhodamine dye is present in the blue colorant composition in the form of particles, but the blue colorant composition has a problem that the dispersion stability is poor and the brightness of the obtained color filter is insufficient.
Therefore, development of a colored photosensitive resin composition capable of producing a color filter having various excellent dispersion stability and luminance has been demanded.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication Nos. 2013-61619 (2013.04.04)
Disclosure of Invention
Problems to be solved
The purpose of the present invention is to provide a colored photosensitive resin composition having excellent dispersion stability and excellent developability.
Another object of the present invention is to provide a color filter and an image display device manufactured using the colored photosensitive resin composition.
Means for solving the problems
The colored photosensitive resin composition of the present invention for achieving the above object is characterized by comprising: a photopolymerizable compound which contains one or more moieties (moieity) selected from the group consisting of ethylene oxide and propylene oxide in a molecular structure and is trifunctional or higher than a urethane acrylic or a structural analogue thereof; a colorant containing a rhodamine-based dye in a particle form; and a dispersant containing a triazine compound.
The color filter and the image display device of the present invention are characterized by containing a cured product of the colored photosensitive resin composition.
Effects of the invention
The colored photosensitive resin composition of the present invention has an advantage that defects such as residues and speckles can be minimized when manufacturing a color filter because of excellent dispersion stability and developability.
In addition, the color filter and the image display device of the present invention have advantages of excellent heat resistance and brightness and excellent driving characteristics by including the cured product of the colored photosensitive resin composition.
Detailed Description
In the present invention, when it is stated that a certain member is "on" another member, it includes not only a case where the certain member is in contact with the another member but also a case where the other member exists between the two members.
In the present invention, when a part is referred to as "including" a certain component, it means that other components may be further included without excluding other components unless otherwise stated.
The present invention will be described in more detail below.
< colored photosensitive resin composition >
The colored photosensitive resin composition according to one embodiment of the present invention has an advantage of excellent dispersion stability by including a photopolymerizable compound that contains one or more moieties (moieity) selected from the group consisting of ethylene oxide and propylene oxide in the molecular structure and is trifunctional or higher than trifunctional urethane acrylic or a structural analog thereof (structural analog), a colorant containing a rhodamine dye in a particle form, and a dispersant containing a triazine compound, and has an advantage of improving the developability, heat resistance, and luminance of a color filter and an image display device manufactured using the composition, and of not generating a residue during development.
Photopolymerizable compound
The colored photosensitive resin composition according to one embodiment of the present invention contains a photopolymerizable compound which contains one or more moieties selected from the group consisting of ethylene oxide and propylene oxide in a molecular structure and is trifunctional or higher than trifunctional urethane acrylic or a structural analog thereof.
According to an embodiment of the present invention, the photopolymerizable compound may be represented by the following chemical formula 1.
[ chemical formula 1]
Figure BDA0001550981400000031
(in the above-mentioned chemical formula 1,
R1selected from the group consisting of hydrogen and methyl,
R2each independently selected from the group consisting of hydrogen and methyl, but not both,
R3selected from the group consisting of-NHCOO-, -COONH-, -NHCONH-, -NHCO-and-SCONH-,
R4selected from the group consisting of aliphatic alkyl group having 3 to 50 carbon atoms, unsaturated alkyl group, cycloalkyl group and aromatic group,
m is an integer of 3 to 12, and n is an integer of 1 to 10).
The photopolymerizable compound according to one embodiment of the present invention is a photopolymerizable compound which contains one or more moieties selected from the group consisting of ethylene oxide and propylene oxide in a molecular structure and is a trifunctional or higher-functional urethane acrylic compound or a structural analog thereof, and has an advantage that it exhibits a higher development rate and does not generate a development residue than a photopolymerizable compound having the same functional group but does not contain an ethylene oxide or propylene oxide moiety.
In the present specification, "urethane acrylic or a structural analog thereof" refers to an acrylic compound containing a urethane group (-NHCOO-) or a urea group (-NHCONH-) or a thiocarbamate group (-NHCO-) as a structural analog thereof.
In the present specification, the "aromatic group" may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, a terphenyl group and the like, and specific examples of the aromatic heterocyclic group include a furyl group, a pyrrolyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrazinyl group, a pyridazinyl group, a triazolyl group, a triazinyl group, an indolyl group, an indazolyl group, a purinyl group, a thiazolinyl group, a thiadiazolyl group, a thiabendazole group, a pyrazolinyl group, a substituted heteroaryl group, and a substituted heteroaryl group, a substituted heteroaryl group,
Figure BDA0001550981400000041
An azolinyl group,
Figure BDA0001550981400000042
Azolyl group,
Figure BDA0001550981400000043
Oxadiazolyl, quinolyl, isoquinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, acridinyl, phenanthrolinyl, phenazinyl, tetrazolyl, benzimidazolyl, benzo
Figure BDA0001550981400000044
Oxazolyl, benzothiazolyl, benzotriazolyl, tetrazolyl (tetrazolindiene), and the like.
The photopolymerizable compound can be produced by reacting a trifunctional or higher isocyanate with a hydroxyl (meth) acrylate obtained by adding at least one selected from the group consisting of ethylene oxide and propylene oxide to (meth) acrylic acid. The photopolymerizable compound may be produced by reacting an acrylic isocyanate with a polyfunctional alcohol to which at least one selected from the group consisting of ethylene oxide and propylene oxide is added.
Specific examples of the above-mentioned hydroxyl (meth) acrylate include hydroxyl mono (meth) acrylate obtained by ring-opening ethylene oxide having 1 to 50 repeating units, and hydroxyl mono (meth) acrylate obtained by ring-opening propylene oxide having 1 to 50 repeating units.
Specific examples of the above-mentioned trifunctional or higher isocyanate include 1, 4-diisocyanatobutane, 1, 6-diisocyanatohexane, 1, 8-diisocyanatooctane, 1, 12-diisocyanatodecane, 1, 5-diisocyanato-2-methylpentane, trimethyl-1, 6-diisocyanatohexane, 1, 3-bis (isocyanatomethyl) cyclohexane, trans-1, 4-cyclohexene diisocyanate, 4' -methylenebis (cyclohexyl diisocyanate), isophorone diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, xylene-1, 4-diisocyanate, tetramethylxylene-1, 3-diisocyanate, 1-chloromethyl-2, 4-diisocyanate, 4 '-methylenebis (2, 6-dimethylphenyl isocyanate), 4' -oxybis (phenyl isocyanate), a trifunctional isocyanate derived from hexamethylene diisocyanate, or a trifunctional isocyanate derived from isophorone diisocyanate.
Specific examples of the polyfunctional alcohol include ethoxylated dipentaerythritol, propoxylated pentaerythritol, and the like.
Specific examples of the acrylic isocyanate include 2- (meth) acryloyloxyethyl isocyanate, 2-isocyanatoethyl acrylate, and the like.
The preferable number of moles of one or more selected from the group consisting of ethylene oxide and propylene oxide added to the photopolymerizable compound of the invention may be 2 to 10 moles. When the number of moles of the oxide added to the above portion is less than 2 moles, the developing speed of the photosensitive resin composition may be decreased, and when the number of moles of the oxide added to the above portion exceeds 10 moles, the curing speed may be decreased, the curing density may be decreased, and physical properties such as surface hardness, heat resistance, and solvent resistance may be decreased. In the polyfunctional monomer represented by chemical formula 1, the urethane bond contained may be in any position in the molecule, but is preferably in the main chain. In the polyfunctional monomer represented by the above chemical formula 1, the number of the acrylic functional groups is not particularly limited, but from the viewpoint of effects, it is more preferable that the polyfunctional monomer contains 3 to 12 acrylic functional groups in a part of the main chain or at the end.
The photopolymerizable compound may further include one or more compounds selected from the group consisting of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and trimethylolpropane tri (meth) acrylate, depending on the purpose of use.
The content of the photopolymerizable compound may be 1 to 60% by weight, preferably 5 to 50% by weight, based on 100% by weight of the total of the alkali-soluble resin and the photopolymerizable compound described later. When the content of the photopolymerizable compound is within the above range, there is an advantage that the development speed is high and no development residue is generated.
Coloring agent
Rhodamine-based dye
The colored photosensitive resin composition according to one embodiment of the present invention contains a colorant containing a rhodamine-based dye in a particle form.
According to an embodiment of the present invention, the rhodamine-based dye may include a dye selected from the group consisting of c.i. acid red 52, 87, 91, 92, 94, 289; c.i. acid yellow 73; c.i. basic red 1; c.i. basic violet 10, 11; and c.i. solvent red 49.
The colored photosensitive resin composition according to one embodiment of the present invention includes a rhodamine-based dye in a particle form, and therefore has an advantage of improving the luminance of a color filter substrate when manufacturing a color filter.
Although not wishing to be bound by theory, in a color filter substrate using a general dye, since the dye is dissolved in the composition, a decrease in contrast due to dry aggregation at the time of prebaking may occur; a decrease in contrast due to oxidation of dye molecules caused by ultraviolet rays upon exposure; and a decrease in contrast due to decomposition, sublimation, or the like of dye molecules during post-baking.
However, in the present invention, since the rhodamine-based dye exists in a particle form, the rhodamine-based dye can stably maintain the particle form even after coating, drying, exposure, development, and post-baking, and therefore, there is an advantage that the luminance of a pixel of a color filter, particularly a blue pixel, is improved and the contrast is excellent.
The rhodamine-based dye may be insoluble in Propylene Glycol Monomethyl Ether Acetate (PGMEA) as an ester-based solvent. The PGMEA is a solvent widely used for coloring photosensitive resin compositions using pigments because it is excellent in stability, coatability, drying property, and dispersion stability of pigments, and is preferable because the rhodamine-based dye is insoluble in the PGMEA, since the above-mentioned characteristics are not impaired, and the pigment and the rhodamine-based dye described later can be stably present in a particle form in the PGMEA.
The rhodamine-based dye is preferably purified to remove ionic impurities contained in the rhodamine-based dye. For example, Na contained in the rhodamine-based dye is preferable+、Cl-、SO4 2-The total amount of such ionic impurities is 20,000ppm or less, and more preferably 10,000ppm or less. Na contained in the rhodamine-based dye+、Cl-、SO4 2-When the total amount of ionic impurities is 20,000ppm or less, there is an advantage that a phenomenon in which dispersion stability is lowered by ionic impurities in the PGMEA can be prevented.
The method for purifying the rhodamine-based dye is not limited to this as long as it is a method generally used in the art, and for example, a reprecipitation method, a recrystallization method, a reverse osmosis membrane method, an ion exchange method using an ion exchange resin (cation exchange resin, anion exchange resin), or the like can be used.
Whether or not the rhodamine-based dye is present in the colored photosensitive resin composition in a Particle form can be confirmed by a Particle size analyzer (Particle size analyzer, accusizer 780A).
In order to find out whether the rhodamine-based dye is in a particle form or a molecular form in the color filter produced from the colored photosensitive resin composition of the present invention, for example, the blue pixel of the color filter can be determined by FIB-TEM analysis and EDX elemental analysis as follows. In the color filter produced as described above, since pigment particles and the rhodamine-based dye particles were mixed together, 100 of these particles were analyzed. The particle diameters of the pigment and the rhodamine dye are 10 to 500nm, and thus the FIB-TEM measurement diameter is 1 to 10 nm. After the FIB-TEM observation, the observation unit was subjected to elemental analysis by EDX. Comparing the EDX analysis results of 100 particles with the EDX analysis results of the rhodamine-based dye itself, if the number of particles having the same analysis result is 1 to 100, it can be determined whether or not the rhodamine-based dye is present in the form of particles in the manufactured color filter.
On the other hand, whether or not the rhodamine-based dye is contained in the colored photosensitive resin composition can be determined by, for example, a laser raman spectroscopy. That is, the pixel is produced by applying the colored photosensitive resin composition, drying with a solvent, exposing, developing, and post-baking. By comparing the laser raman spectrum of the pixel thus produced with the laser raman spectrum of the rhodamine-based dye itself, it is possible to determine whether or not the rhodamine-based dye is contained in the colored photosensitive resin composition.
The average particle diameter of the rhodamine dye and the pigment described later is preferably 30 to 200nm, and more preferably 30 to 100 nm. When the average particle size of the rhodamine-based dye and a dye described later exceeds 200nm, the transmittance and contrast may be reduced by scattering of particles, and when the average particle size of the rhodamine-based dye is less than 30nm, the alkali solubility of the binder resin in unexposed portions may be reduced, and the pattern processability may be reduced.
The average particle diameters of the rhodamine dye and the pigment described later can be adjusted to the above ranges by applying a shear stress to the rhodamine dye and the pigment described later via zirconia beads by a dispersing machine such as a sand mill or a ball mill.
However, it may be difficult to adjust the average particle diameter of the rhodamine-based dye to the above range under the dispersion conditions of the conventionally known pigments. For example, the pigment powder is a powder particle of several μm formed by collecting 1-time particles of about 30 nm. Since the pigment powder has a small cohesive force between 1 st order particles, the pigment powder can disperse the cohesive force of 1 st order particles by a small shear stress and short-time dispersion, and the average particle diameter is 30 to 200 nm. However, the dye powder is a coarse particle of several μm formed by aggregation of molecules of about 1 nm. Since the dye powder has a strong intermolecular cohesive force, it is difficult to reduce the average particle diameter to less than 200nm by a small shear stress. Further, 1 st order particles are not present in the dye, and thus if shear stress is increased or dispersion time is increased, the average particle diameter may be less than 30 nm.
Therefore, in order to set the average particle diameter of the rhodamine-based dye and the pigment described later to 30 to 200nm, it is preferable to disperse the rhodamine-based dye and the pigment under different dispersion conditions.
The rhodamine-based dye is preferably dispersed with zirconia beads having a bead diameter of 0.3 to 2.0 μm under a large shear stress for a dispersion time of 3 to 10 hours/kg, and the pigment is preferably dispersed with zirconia beads having a bead diameter of 0.1 to 2.0 μm for a dispersion time of 1 to 10 hours/kg.
In the present invention, it is preferable to additionally perform a dispersing process after mixing the rhodamine-based dye dispersion and the pigment dispersion which have undergone the respective dispersing processes. This process can adjust the average particle diameters of the rhodamine-based dye and the pigment to a range of 30 to 100nm, and can improve the transmittance and the brightness to further improve the contrast.
As the additional dispersion conditions of the mixed dispersion, it is preferable to disperse zirconia balls having a ball diameter of 0.01 to 0.2 μm with a small shear stress and a dispersion time of 0.1 to 3 hours/kg.
In addition, since the colored photosensitive resin composition according to one embodiment of the present invention contains both the rhodamine-based dye for dispersion stabilization in the composition and the dispersant containing the triazine-based compound, there is an advantage that the luminance can be further improved and the contrast can be prevented from being lowered, as compared with the case where the rhodamine-based dye is contained alone.
The rhodamine-based dye may be contained in an amount of 1 to 80 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the entire colorant dispersion. When the content of the rhodamine-based dye is within the above range, the content is preferably in view of dispersion stability and transmittance. When the content of the rhodamine-based dye is less than the above range, the transmittance may be decreased, and when the content exceeds the above range, the dispersion stability may be decreased by aggregation of the dye.
Pigment (I)
The colored photosensitive resin composition according to an embodiment of the present invention may contain a pigment together with the rhodamine-based dye.
The pigment may be an organic pigment or an inorganic pigment generally used in the art. The pigment may be any of various pigments used in printing inks, inkjet inks, and the like, and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, and bisperylene pigments
Figure BDA0001550981400000081
Oxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone (anthanthrone) pigments, indanthrone (indanthrone) pigments, flavanthrone pigments, pyranthrone (pyranthrone) pigments, diketopyrrolopyrrole pigments, and the like, but are not limited thereto.
Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specific examples thereof include metal oxides and composite metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black, but the inorganic pigment is not limited thereto.
In particular, as The organic pigment and The inorganic pigment, specifically, compounds classified as pigments in color index (published by The society of Dyers and Colourists), more specifically, pigments numbered by The following color index (c.i.) are mentioned, but not limited thereto, and they may be used alone or in combination of two or more kinds.
C.i. pigment yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185;
c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71;
c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, 264;
c.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37, 38;
c.i. pigment blue 15(15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, 76;
c.i. pigment green 7, 10, 15, 25, 36, 47, 58, 59, 62, 63;
c.i. pigment brown 28;
c.i. pigment black 1, 7; etc. of
The above pigments may be used each alone or in combination of two or more.
Among the above-exemplified c.i. pigments, pigments selected from the group consisting of c.i. pigment orange 38, c.i. pigment red 122, c.i. pigment red 166, c.i. pigment red 177, c.i. pigment red 208, c.i. pigment red 242, c.i. pigment red 254, c.i. pigment red 255, c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150, c.i. pigment yellow 185, c.i. pigment green 7, c.i. pigment green 36, c.i. pigment green 58, c.i. pigment violet 23, c.i. pigment blue 15:3, and pigment blue 15:6 can be preferably used.
The pigment is preferably a colorant dispersion liquid in which the particle diameter is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment by adding a pigment dispersant, and a colorant dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained by this method, and therefore, this method is preferable.
The pigment dispersant may be added separately from a triazine compound-containing dispersant described later, and examples thereof include cationic, anionic, nonionic, zwitterionic, polyester, polyamine, and other surfactants, and these may be used alone or in combination of two or more.
The content of the pigment is in the range of 1 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the entire colorant dispersion. The content of the pigment is preferably in the range of 1 to 50 parts by weight based on the above, because the viscosity is low, the storage stability is excellent, the dispersion efficiency is high, and the effect of improving the contrast is high.
In addition, the colorant dispersion liquid may further contain a dispersion medium.
The dispersion medium is added for the purpose of disaggregation of the pigment and maintenance of stability, and a dispersion medium generally used in the art can be used without limitation. Preferably, an acrylate-based dispersant (hereinafter, referred to as an acrylic dispersant) containing Butyl Methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) is preferable. In this case, the acrylic dispersant is preferably manufactured by the activity control method disclosed in Korean laid-open patent No. 2004-0014311, and examples of commercially available acrylic dispersants manufactured by the activity control method include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.
The above-exemplified acrylic dispersants may be used each alone or in combination of two or more.
The dispersion medium may be a resin type pigment dispersant other than the acrylic dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, and particularly oil-based dispersants such as polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or amides or salts thereof formed by reaction of polyesters having free (free) carboxyl groups with poly (lower alkylene imine); water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinyl pyrrolidone; a polyester; a modified polyacrylate; an ethylene oxide/propylene oxide adduct; and phosphoric acid esters and the like. As a commercial product of the above resin type pigment dispersant, for example, a trade name of BYK chemical company: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, and DISPER BYK-184; trade name of BASF (BASF) corporation: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; trade name of Lubirzol (lubol) corporation: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Chuanjian refining company: HINACT T-6000, HINACT T-7000, HINACT T-8000; trade name of ajinomoto corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; trade name of Kyoeisha chemical Co: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc. The resin type pigment dispersants other than the above-mentioned acrylic dispersant may be used alone or in combination of two or more kinds, or may be used in combination with the acrylic dispersant.
The content of the pigment dispersant may be 0.1 to 30 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. When the content of the pigment dispersant satisfies the above range, the contrast and stability can be improved.
Dispersant containing triazine compound
The colored photosensitive resin composition according to one embodiment of the present invention contains a dispersant containing a triazine compound. The triazine compound is not limited to the above-mentioned one as long as it is known as a dispersant in the art. For example, triazine dispersants described in Japanese patent laid-open No. 2008-214515 and Japanese patent laid-open No. 2011-032374 can be used.
According to an embodiment of the present invention, the triazine compound may be represented by the following chemical formula 2.
[ chemical formula 2]
Figure BDA0001550981400000111
(in the above-mentioned chemical formula 2,
R5selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a straight or branched alkoxy group having 1 to 20 carbon atoms and-NR6R7A group of radicals, and (b) a group of radicals,
R6and R7Each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms,
in this case, the alkyl group and the alkoxy group are substituted or unsubstituted with a hydroxyl group or a linear or branched alkoxy group having 1 to 20 carbon atoms. )
In the chemical formula 2, specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a sec-propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group, and specific examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a sec-propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.
When the triazine compound is contained, the pigment and the rhodamine dye can be uniformly dispersed in various media. Therefore, the colored photosensitive resin composition according to one embodiment of the present invention has an advantage that the colored photosensitive resin composition contains the dispersant containing the triazine compound, thereby suppressing the reaggregation and the increase in viscosity of the rhodamine dye-containing colorant, and improving the storage stability.
In addition, when the triazine compound is used in combination with a resin-type dispersant in the dispersant, the effect of improving the dispersibility of the rhodamine-based dye and the pigment and the effect of inhibiting reaggregation can be particularly remarkable.
Further, since the triazine compound exhibits white color in the visible region, an image display device capable of high-brightness color development can be produced by using a color filter formed from a colored photosensitive resin composition containing the triazine compound. The colored photosensitive resin composition produced using the triazine compound has a low initial viscosity and a high effect of suppressing the re-aggregation of the pigment, and therefore has the advantages of excellent storage stability of the dispersant and a small increase in viscosity due to storage.
The triazine compound may be contained in an amount of 0.1 to 60 parts by weight based on 100 parts by weight of the entire colorant. When the content of the triazine compound is within the above range, crystal growth of the rhodamine dye and the pigment can be suppressed, and therefore, the triazine compound is preferable. When the content of the triazine compound is less than the above range, the rhodamine dye may aggregate, and when the content exceeds the above range, the contrast may decrease.
The colored photosensitive resin composition according to an embodiment of the present invention may further include one or more selected from the group consisting of an alkali-soluble resin, a photopolymerization initiator, a solvent, and an additive.
Alkali soluble resin
The colored photosensitive resin composition according to an embodiment of the present invention may further include an alkali-soluble resin.
The alkali-soluble resin is a component which is polymerized by including an ethylenically unsaturated monomer having a carboxyl group and which imparts solubility to an alkali developer used in a developing process in forming a pattern.
The ethylenically unsaturated monomer having a carboxyl group is not particularly limited, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid, and anhydrides thereof; and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxy polycaprolactone mono (meth) acrylate, and preferably acrylic acid or methacrylic acid. These may be used alone or in combination of two or more.
The alkali-soluble resin may further include at least one other monomer copolymerizable with the monomer. For example, there may be mentioned aromatic vinyl compounds such as styrene, vinyltoluene, methylstyrene, 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 and p-vinylbenzyl glycidyl ether; n-substituted maleimide compounds such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide and N-p-methoxyphenylmaleimide; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate; alicyclic (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; unsaturated oxetane compounds such as 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like. These may be used alone or in combination of two or more.
In the present specification, (meth) acrylate means acrylate or methacrylate.
The content of the alkali-soluble resin is not particularly limited, and is, for example, preferably 5 to 80% by weight, more preferably 10 to 70% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, the solubility in a developer is sufficient to facilitate pattern formation, and the peeling of non-pixel portions can be improved by preventing the film of pixel portions in exposed portions from being reduced during development.
Photopolymerization initiator
The colored photosensitive resin composition according to an embodiment of the present invention may further include a photopolymerization initiator.
The photopolymerization initiator may be used without particular limitation as long as it is a compound used as a photopolymerization initiator in the art, but preferably includes one or more selected from the group consisting of triazine-based compounds, acetophenone-based compounds, biimidazole-based compounds, and oxime compounds. When the colored photosensitive resin composition contains the photopolymerization initiator, the sensitivity is improved, and the strength or the pattern of the pixel portion of the pixel formed by the composition is improved.
Further, if a photopolymerization initiator is used in combination with a photopolymerization initiator, the sensitivity of a photosensitive resin composition containing these compounds is increased, and the productivity in forming a color filter using the composition can be improved.
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) vinyl ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl ] -1,3, 5-triazine ) 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.
As the acetophenone-based compound, for example, examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one.
Examples of the biimidazole compound include 2,2 ' -bis (2-chlorophenyl) -4,4,5,5 ' -tetraphenylbiimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4, 4', 5,5 ' -tetraphenylbiimidazole, 2 ' -bis (2-chlorophenyl) -4, 4', 5,5 ' -tetrakis (alkoxyphenyl) biimidazole, 2 ' -bis (2-chlorophenyl) -4, 4', 5,5 ' -tetrakis (trialkoxyphenyl) biimidazole, and imidazole compounds in which the phenyl group at the 4,4', 5,5 ' position is substituted with an alkoxycarbonylacyl group. Among them, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole and 2, 2' -bis (2, 3-dichlorophenyl) -4, 4', 5, 5' -tetraphenylbiimidazole are preferably used.
Specific examples of the photopolymerization initiator other than the photopolymerization initiator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and anthracene compounds. They may be used each alone or in combination of two or more.
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, 2,4, 6-trimethylbenzophenone, and 4,4' -bis (N, N ' -dimethylamino) benzophenone.
Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
Examples of the anthracene compound include 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, and 2-ethyl-9, 10-diethoxyanthracene.
Besides, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9, 10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. can be used as the photopolymerization initiator.
In addition, as the photopolymerization initiation aid that can be used in combination with the photopolymerization initiator in the present invention, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and the like can be preferably used.
Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine and the like; aromatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N-dimethyl-p-toluidine, 4 ' -bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4 ' -bis (diethylamino) benzophenone. As the amine compound, an aromatic amine compound is preferably used.
Specific examples of the carboxylic acid compound include aromatic heteroacetates such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthyloxyacetic acid.
The content of the photopolymerization initiator is preferably 0.1 to 20% by weight, more preferably 1 to 12% by weight, based on 100% by weight of the total solid content of the colored photosensitive resin composition containing the photopolymerization initiator. When the content of the photopolymerization initiator is within the above range, the colored photosensitive resin composition containing the photopolymerization initiator can be highly sensitive and can provide excellent strength of the pixel portion and surface smoothness of the pixel portion.
The content of the photopolymerization initiator is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on 100% by weight of the total solid content of the colored photosensitive resin composition. If the content of the photopolymerization initiation aid is within the above range, the sensitivity efficiency of the colored photosensitive resin composition containing the photopolymerization initiation aid is further improved, and the productivity of a color filter formed using the composition can be improved.
Solvent(s)
The colored photosensitive resin composition according to an embodiment of the present invention may further contain a solvent.
The solvent is not particularly limited as long as it is a solvent used in the art, and various organic solvents can be used.
Specific examples of the 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; 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 and propylene glycol monopropyl ether acetate; alkoxyalkyl acetates such as 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.
From the viewpoint of coating properties and drying properties, the solvent preferably includes an organic solvent having a boiling point of 100 to 200 ℃ among the solvents, more preferably alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and further preferably includes propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. These solvents may be used either individually or as a mixture of two or more thereof.
The content of the solvent is preferably 60 to 90% by weight, more preferably 70 to 85% by weight, based on 100% by weight of the entire colored photosensitive resin composition containing the solvent. When the content of the solvent is within the above range, the coating properties are improved when the coating is performed using a coating device such as a roll coater, a spin coater, a slit coater (also referred to as a die coater), or an ink jet printer.
Additive agent
The colored photosensitive resin composition according to an embodiment of the present invention may further contain an additive.
The additives may be optionally added as needed, and examples thereof include other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-gelling agents.
Specific examples of the other polymer compound include, but are not limited to, curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
The curing agent is used for achieving deep curing and improving mechanical strength, and specific examples thereof include, but are not limited to, epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.
More specific examples of the epoxy compound in the curing agent include bisphenol a type epoxy resins, hydrogenated bisphenol a type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol F type epoxy resins, novolac type epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester type resins, glycidyl amine type resins, brominated derivatives of the above epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, epoxides of butadiene (co) polymers, epoxides of isoprene (co) polymers, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.
More specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane and cyclohexanedicarboxylate bisoxetane.
The curing agent may be used in combination with a co-curing compound capable of ring-opening polymerizing an epoxy group of the epoxy compound or an oxetane skeleton of the oxetane compound together with the curing agent.
Examples of the curing assistant compound include polycarboxylic acids, polycarboxylic acid anhydrides, and acid generators. The polycarboxylic acid anhydride may be a commercially available epoxy resin curing agent. Examples of commercially available products include ADEKA HARDENER EH-700 (manufactured by ADEKA industries, Ltd.), RIKACID HH (manufactured by Nissian laboratories, Ltd.), and MH-700 (manufactured by Nissian laboratories, Ltd.). The curing agent and the co-curing compound may be used either individually or as a mixture of two or more thereof.
The surfactant may be used for further improving the film formation of the colored photosensitive resin composition, and preferably, a silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, or zwitterionic surfactant may be used.
Examples of the silicone surfactants include commercially available silicone surfactants such as DC3PA, DC7PA, SH11PA, SH21PA and SH8400 available from KANGNING DONGLI Silicone Co., Ltd, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 available from GE Toshiba Silicone Co., Ltd.
Examples of the above-mentioned fluorine-based surfactant include MEGAFAC F-470, F-471, F-475, F-482 and F-489, which are commercially available from Dainippon ink chemical industries, Inc.
Further, other commercially available products that can be used include KP (shin-Etsu chemical industry, Inc.), polyfow (Country chemical Co., Ltd.), EFTOP (Tokheim product Co., Ltd.), MEGAFAC (Japan ink chemical industry, Inc.), Flourad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (manufactured by Asahi glass Co., Ltd.), SOLSPERSE (Lumbou), EFKA (EFKA chemical Co., Ltd.), PB 821 (monosodium glutamate (Co., Ltd.), Disperbyk series (Pico chemical), and the like.
Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.
Examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkylaryl sulfonate salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene derivatives, ethylene oxide/propylene oxide block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene alkylamines, and the like.
The above surfactants may be used each alone or in combination of two or more.
The kind of the adhesion promoter is not particularly limited, and specific examples of usable 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, and the like, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like.
The adhesion promoters may be used singly or in combination of two or more. The content of the adhesion promoter may be usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.
The type of the antioxidant is not particularly limited, but examples thereof include 2,2' -thiobis (4-methyl-6-tert-butylphenol), 2, 6-di-tert-butyl-4-methylphenol and the like.
The kind of the ultraviolet absorber is not particularly limited, and specific examples thereof include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
The kind of the above-mentioned anti-gelling agent is not particularly limited, and specific examples thereof include sodium polyacrylate and the like.
< color Filter >
Another embodiment of the present invention relates to a color filter which is manufactured using the colored photosensitive resin composition, and has excellent developability and heat resistance, improved brightness, and no residue during development.
The color filter includes a substrate and a pattern layer formed on the substrate.
The substrate is not particularly limited, and the color filter itself may be a substrate, or may be a portion where the color filter is located in a display device or the like. 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 formed by applying the colored photosensitive resin composition and exposing, developing, and thermally curing the applied layer in a predetermined pattern, as a layer containing the colored photosensitive resin composition of the present invention. The above-described pattern layer may be formed by performing a method generally known in the art.
The color filter including the substrate and the pattern layer may further include a partition wall formed between the patterns, or may further include a black matrix, but is not limited thereto.
In addition, the color filter may further include a protective film formed on the upper portion of the pattern layer of the color filter.
< image display apparatus >
In addition, another embodiment of the present invention relates to an image display device including the color filter, which has excellent developability and heat resistance, improves brightness, and does not generate residue during development.
The image display device of the present invention includes the color filter, and specific examples thereof include, but are not limited to, a liquid crystal display, an OLED, a flexible display, and the like.
Hereinafter, preferred embodiments are disclosed to aid understanding of the present invention, but the following embodiments are merely illustrative of the present invention, and various changes and modifications, which are obvious to those skilled in the art, may be made within the scope and technical spirit of the present invention, and such changes and modifications naturally fall within the scope of the appended claims. In the following examples and comparative examples, "%" and "part(s)" representing the content are based on weight unless otherwise specifically mentioned.
Synthesis example
Synthesis example 1: triazine compound 1
To 100 parts by weight of water were added 18.4 parts by weight of 2-chloro-4, 6-diamino-1, 3, 5-triazine and 21 parts by weight of 3- (2-ethylhexyloxy) propylamine, and the mixture was reacted at 10 ℃ for 1 hour. The resultant reaction was allowed to react at 85 ℃ for 5 hours. The residue obtained by leaching the obtained reaction product is washed with water, and then left to stand overnight in a thermostatic bath at 100 ℃ for drying, thereby obtaining a compound of the following chemical formula 3.
[ chemical formula 3]
Figure BDA0001550981400000201
Synthesis example 2: triazine compound 2
To 100 parts by weight of water were added 18.4 parts by weight of 2-chloro-4, 6-diamino-1, 3, 5-triazine and 21 parts by weight of butylamine, and the mixture was reacted at 10 ℃ for 1 hour. The resultant reaction was allowed to react at 85 ℃ for 5 hours. The residue obtained by leaching the obtained reaction product is washed with water, and then left to stand overnight in a thermostatic bath at 100 ℃ for drying, thereby obtaining a compound of the following chemical formula 4.
[ chemical formula 4]
Figure BDA0001550981400000211
Synthesis example 3: trifunctional Compound (B-1) to which ethylene oxide has been added
In a 0.5L three-port reactor equipped with a mechanical stirrer, a thermometer and a condenser, 128.5 parts by weight (0.22 mol) of an isocyanurate type oligomer of hexamethylene diisocyanate (Bayer Co., N3300), 271.4 parts by weight (0.81 mol) of polyethylene glycol monoacrylate (Corning Co., Bisomer PEA6) and 0.1 part by weight of methoxyhydroquinone (HQMME, Ischman Co.) were charged and stirred at normal temperature. The reaction mixture was allowed to self-heat until the reaction temperature reached 105 ℃ and was measured by FT-IR after 4 hours, confirming 2260cm- 1The reaction was terminated after complete disappearance.
Synthesis example 4: hexafunctional compound (B-2) to which ethylene oxide is added
Adding 2-acrylic acid isocyano in a 0.5L three-port reactor provided with a mechanical stirrer, a thermometer and a condenser282.24 parts by weight (2 moles) of acid ethyl ester (AOI-VM, Showa Denko K.K.), 103.66 parts by weight (0.2 moles) of ethoxylated dipentaerythritol (Sigma Aldrich, CAS 30599-15-6), and 0.2 parts by weight of methoxyhydroquinone (HQMME, Istman K.) were added, and the mixture was stirred at room temperature. The reaction mixture was allowed to self-heat until the reaction temperature reached 105 ℃ and was measured by FT-IR after 6 hours, confirming 2260cm-1The reaction was terminated after complete disappearance.
Synthesis example 5: resin composition
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube was prepared, while a monomer dropping funnel was prepared by charging 74.8g (0.20 mol) of benzylmaleimide, 43.2g (0.30 mol) of acrylic acid, 118.0g (0.50 mol) of vinyltoluene, 4g of t-butyl peroxy-2-ethylhexanoate and 40g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) and mixing them under stirring, and a chain transfer agent dropping vessel was prepared by charging 6g of n-dodecanethiol and 24g of PGMEA and mixing them under stirring. Thereafter, 395g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and then the temperature of the flask was raised to 90 ℃ while stirring. Subsequently, the monomer and the chain transfer agent were added dropwise 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 a mixed gas of 5/95(v/v) with oxygen/nitrogen. Subsequently, 28.4g of glycidyl methacrylate [ (0.10 mol%) ], 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 an alkali-soluble resin having a solid acid value of 70 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.
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:
Figure BDA0001550981400000221
injection amount:
Figure BDA0001550981400000222
a detector: RI (Ri)
And (3) measuring the concentration of the sample: 0.6% by mass (solvent ═ tetrahydrofuran)
Calibration standard substance: TSK Standard polystyrenes F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh corporation)
The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as the molecular weight distribution (Mw/Mn).
Production example
Production example 1: colorant Dispersion 1(A-1)
20.48 parts by weight of the compound of chemical formula 3 synthesized in Synthesis example 1 as a triazine derivative, 9.12 parts by weight of C.I. pigment blue 15:6, 2.88 parts by weight of C.I. acid Red 52, 3.84 parts by weight of an acrylic dispersant (DisperbyK-2000, manufactured by Bikk Co., Ltd.), 2.88 parts by weight of the resin of Synthesis example 5, 55.04 parts by weight of propylene glycol monomethyl ether acetate and 5.76 parts by weight of propylene glycol monomethyl ether as solvents, and 360 parts by weight of zirconia balls having a diameter of 0.2mm were put into a mayonnaise bottle having a capacity of 140ml, and kneaded at 60 ℃ for 10 hours by a paint conditioner to conduct dispersion treatment. Thereafter, the zirconia balls were removed to obtain a dispersion. The dispersion was filtered through a membrane filter having a pore size of 1.0. mu.m, to obtain a colorant dispersion 1.
Production example 2: colorant Dispersion 2(A-2)
The preparation of triazine derivative of chemical formula 4 was performed in the same manner as in preparation example 1, except that the compound was synthesized in preparation example 2.
Production example 3: colorant Dispersion 3(A-3)
The same procedure as in production example 1 was repeated except that the triazine derivative was not used.
Production example 4: colorant Dispersion 4(A-4)
The same procedure as in production example 1 was repeated except that c.i. pigment violet 23 was used instead of acid red 52.
Examples and comparative examples
Colored photosensitive resin compositions of examples and comparative examples were prepared according to the compositions shown in table 1 below.
[ Table 1]
Figure BDA0001550981400000231
Examples of the experiments
Experimental example 1: measurement of luminance
After applying the colored photosensitive resin composition solutions of the examples and comparative examples on a glass substrate, the glass substrate was pretreated by baking the glass substrate on a hot plate at 90 ℃ for 3 minutes, a test photomask having a circular pattern with a diameter of 1 to 50 μm was placed thereon, and the test photomask was irradiated with ultraviolet rays with a distance of 100 μm. In this case, a 1KW high pressure mercury lamp containing three rays of g, h and i was used as the ultraviolet light source at a dose of 100mJ/cm2No special optical filter was used for the irradiation. The film irradiated with ultraviolet rays was developed with a KOH aqueous solution developing solution having a pH of 10.5, and then baked at 230 ℃/20 min. Thereafter, the sample was set in a spectrophotometer (trade name: CM-3700d, product of Konika Minkoda sensor Co., Ltd.) to measure the transmitted chromaticity on the X, Y, Z coordinate axis at 2 ℃ C light source, and the Y value at this time was used as the luminance. The results are shown in table 2 below.
The luminance values shown in table 2 below are relative values when the luminance of a color filter produced using the colored photosensitive resin composition of comparative example 1 is defined as a standard (100).
Experimental example 2: measurement of Heat resistance
After applying the colored photosensitive resin composition solutions of the examples and comparative examples on a glass substrate, the glass substrate was pretreated by baking the glass substrate on a hot plate at 90 ℃ for 3 minutes, a test photomask having a circular pattern with a diameter of 1 to 50 μm was placed thereon, and the test photomask was irradiated with ultraviolet rays with a distance of 100 μm. In this case, a 1KW high pressure mercury lamp containing three rays of g, h and i was used as the ultraviolet light source at a dose of 100mJ/cm2No special optical filter was used for the irradiation. The film irradiated with ultraviolet rays was developed with a KOH aqueous solution developing solution having a pH of 10.5, and then baked at 230 ℃/20 min. The color filter was further baked at 230 ℃/2hr, and the color difference before and after baking was evaluated. A color filter was placed in a spectrocolorimeter (CM-3700d, product of Konika Minton Co., Ltd.) and the values of L, a, and b were measured at 2 ℃ C light source. The color difference in the three-dimensional colorimeter defined by L, a, b is according to [ mathematical formula 1 ]It is calculated that the smaller the color difference value, the more reliable the color filter can be manufactured. The results are shown in table 2 below.
[ mathematical formula 1]
△Eab*＝[(△L*)2+(△a*)2+(△b*)2]1/2
Experimental example 3: development speed measurement
After applying the colored photosensitive resin composition solutions of the examples and comparative examples on a glass substrate, the glass substrate was pretreated by baking the glass substrate on a hot plate at 90 ℃ for 3 minutes, a test photomask having a circular pattern with a diameter of 1 to 50 μm was placed thereon, and the test photomask was irradiated with ultraviolet rays with a distance of 100 μm. In this case, a 1KW high pressure mercury lamp containing three rays of g, h and i was used as the ultraviolet light source at a dose of 100mJ/cm2No special optical filter was used for the irradiation. The film irradiated with ultraviolet rays was developed with a KOH aqueous solution developing solution having a pH of 10.5. The minimum development time during which a pattern can be formed and the non-exposed portion is free from residue was determined as the development speed, whichThe results are shown in Table 2 below.
Experimental example 4: measurement of development residue
The colored photosensitive resin compositions produced in the examples and comparative examples were applied to 5X 5cm of glass, dried, and then applied to a thickness of 2.5. mu.m. Thereafter, the resultant was dried in an oven at 100 ℃ for 5 minutes to remove the solvent, and then immersed in an aqueous KOH solution having a pH of 10.5 for 1 minute, taken out, observed with a surface inspection lamp (FR-100R), and then inspected according to the following criteria, and the results are shown in table 2 below.
< evaluation criteria >
< evaluation criteria for residue >
O: no resin residue on the surface was observed
And (delta): surface resin residue was seen but not noticeably
X: the surface resin residue was clearly seen with naked eyes
[ Table 2]
Brightness of light Heat resistance Developing speed Residue of rice
Example 1 1.12 1.21 15 ○
Example 2 1.08 1.23 16 ○
Example 3 1.1 1.31 10 ○
Example 4 1.07 1.33 8 ○
Example 5 1.09 1.32 5 ○
Comparative example 1 1 3.55 17 △
Comparative example 2 1.07 2.14 30 ×
Comparative example 3 0.95 3.67 36 ×
Comparative example 4 0.6 1.36 15 ○
Referring to table 2 above, it was confirmed that in the case of examples 1 to 5 of the present invention containing a colorant containing a rhodamine-based dye in a particle form, a dispersant containing a triazine-based compound, and a photopolymerizable compound containing an ethylene oxide-added compound, the luminance, heat resistance, and developability were all more excellent than those of comparative example 1 not containing a dispersant containing a triazine-based compound and comparative examples 2 to 3 not containing a photopolymerizable compound containing an ethylene oxide-added compound, and the luminance was more excellent than that of comparative example 4 not containing a rhodamine-based dye.

Claims (8)

1. A colored photosensitive resin composition, comprising:
a photopolymerizable compound which is a trifunctional or higher urethane acrylic or a structural analog thereof and contains one or more moieties selected from the group consisting of ethylene oxide and propylene oxide in a molecular structure;
A colorant containing a rhodamine-based dye in a particle form; and
a dispersant containing a triazine compound, which is a compound having a triazine group,
the triazine-based compound is represented by the following chemical formula 2:
chemical formula 2
Figure FDA0003133529650000011
In the chemical formula 2, the first and second organic solvents,
R5is-NR6R7The base group is a group of a compound,
R6and R7Each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms,
in this case, the alkyl group is substituted or unsubstituted with a hydroxyl group or a linear or branched alkoxy group having 1 to 20 carbon atoms.
2. The colored photosensitive resin composition according to claim 1, further comprising one or more selected from the group consisting of an alkali-soluble resin, a photopolymerization initiator, a solvent, and an additive.
3. The colored photosensitive resin composition according to claim 1, wherein the photopolymerizable compound is represented by the following chemical formula 1:
chemical formula 1
Figure FDA0003133529650000012
In the chemical formula 1, the metal oxide is represented by,
R1selected from the group consisting of hydrogen and methyl,
R2each independently selected from the group consisting of hydrogen and methyl, but not both,
R3selected from the group consisting of-NHCOO-, -COONH-, -NHCONH-, -NHCO-and-SCONH-,
R4selected from the group consisting of aliphatic alkyl group having 3 to 50 carbon atoms, unsaturated alkyl group, cycloalkyl group and aromatic group,
m is an integer of 3 to 12, and n is an integer of 1 to 10.
4. The colored photosensitive resin composition according to claim 1, wherein the photopolymerizable compound is contained in an amount of 1 to 60 wt% based on 100 wt% of the total of the alkali-soluble resin and the photopolymerizable compound.
5. The colored photosensitive resin composition according to claim 1, wherein the rhodamine-based dye comprises a dye selected from the group consisting of c.i. acid red 52, 87, 91, 92, 94, 289; c.i. acid yellow 73; c.i. basic red 1; c.i. basic violet 10, 11; and c.i. solvent red 49.
6. The colored photosensitive resin composition according to claim 1, wherein the colorant further comprises a pigment.
7. A color filter comprising a cured product of the colored photosensitive resin composition according to any one of claims 1 to 6.
8. An image display device comprising the color filter of claim 7.
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