CN107239004B - Colored photosensitive resin composition, color filter and image display device manufactured using the same - Google Patents
Colored photosensitive resin composition, color filter and image display device manufactured using the same Download PDFInfo
- Publication number
- CN107239004B CN107239004B CN201710016692.2A CN201710016692A CN107239004B CN 107239004 B CN107239004 B CN 107239004B CN 201710016692 A CN201710016692 A CN 201710016692A CN 107239004 B CN107239004 B CN 107239004B
- Authority
- CN
- China
- Prior art keywords
- photosensitive resin
- resin composition
- colored photosensitive
- pigment
- rhodamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
-
- 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
- C09B41/00—Special methods of performing the coupling reaction
- C09B41/001—Special methods of performing the coupling reaction characterised by the coupling medium
- C09B41/005—Special methods of performing the coupling reaction characterised by the coupling medium containing low molecular weight dispersing agents; containing surface active polythylene gylcols
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- 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
- G03F7/0005—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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Engineering & Computer Science (AREA)
- Mathematical Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
Abstract
The present invention relates to a colored photosensitive resin composition, and particularly, to a colored photosensitive resin composition, a color filter and an image display device manufactured using the same, the colored photosensitive resin composition comprising: a colorant comprising a rhodamine-based dye and a pigment in a particle state; and a dispersant containing a triazine-based compound.
Description
Technical Field
The present invention relates to a colored photosensitive resin composition, a color filter and an image display device manufactured 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 composed of three color patterns of Red (Red), Green (Green), and Blue (Blue), or three color patterns of Yellow (Yellow), Magenta (Magenta), and Cyan (Cyan).
The color filter widely used in the above display device is generally manufactured by: the color filter is manufactured by uniformly applying a colored photosensitive resin composition containing a pigment dispersion composition of colors corresponding to respective patterns on a substrate on which black matrix patterns are formed by spin coating or slit coating, exposing and developing the coating film formed by heat drying, and additionally heating and curing as needed, and repeating the above operations for each color to form pixels of each color.
A color filter using such a colored photosensitive resin composition is required to have physical properties such as high brightness and high contrast, and recently, a pixel having high color reproducibility is required. Thereby, the content of the pigment and the carbon black of the coloring material used in the colored resin composition is increased. However, when the content of the coloring material in the colored resin composition is increased, there are problems as follows: in order to exhibit excellent optical characteristics, it is necessary to micronize the pigment, and particularly, the viscosity is increased when a high-concentration pigment dispersion composition is produced, or the storage stability such as gelation of the pigment dispersion composition during storage is deteriorated, thereby also deteriorating the optical characteristics such as brightness and contrast.
Jp 2013 a 61619 a relates to a cyan colorant composition for a color filter and a color filter substrate using the same, and discloses a cyan colorant composition for a color filter, which contains at least a colorant, a binder resin, a polymer dispersant and a solvent, and is characterized in that the colorant contains a pigment and a rhodamine-based dye, and the rhodamine-based dye is present in the cyan colorant composition in a particle state, and actually, the dispersion stability is not excellent, and the contrast is slightly difficult to be applied to a high-quality color filter.
Therefore, it is required to develop various colored photosensitive resin compositions which have excellent dispersion stability and can produce high-quality color filters having high contrast.
Documents of the prior art
Patent document 1: japanese patent laid-open publication No. 2013-61619 (2013.04.04)
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a colored photosensitive resin composition which has excellent dispersion stability and can produce a color filter having excellent developability, heat resistance, solvent resistance, contrast, or brightness.
In addition, the present invention is to provide a color filter and an image display device manufactured by using the colored photosensitive resin composition.
Means for solving the problems
The colored photosensitive resin composition according to the present invention for achieving the above object is characterized by comprising: a rhodamine-based dye present in a particle state; a dispersant comprising a triazine-based compound; and a pigment.
In addition, the present invention provides a color filter produced from the colored photosensitive resin composition and an image display device comprising the same.
ADVANTAGEOUS EFFECTS OF INVENTION
The colored photosensitive resin composition of the present invention can provide a colored photosensitive resin composition having excellent dispersion stability.
In addition, the color filter produced by using the colored photosensitive resin composition of the present invention and an image display device comprising the color filter have the advantages of excellent developability, heat resistance, solvent resistance, contrast and brightness.
Detailed Description
The present invention will be described in detail below.
In the present invention, when a certain member is "on" another member, it includes not only a case where the certain member is in contact with the other member but also a case where another member exists between the two members.
In the present invention, when a certain portion "includes" a certain component, it does not exclude other components unless specifically stated to the contrary, but means that other components can be included.
< colored photosensitive resin composition >
One aspect of the present invention relates to a colored photosensitive resin composition comprising: a colorant comprising a rhodamine-based dye and a pigment in a particle state; and a dispersant containing a triazine-based compound. In one embodiment, the present invention relates to a cyan colored photosensitive resin composition comprising: a colorant comprising a rhodamine-based dye and a pigment in a particle state; and a dispersant containing a triazine-based compound.
The colorant of the present invention comprises a rhodamine-based dye and a pigment in a particle state.
Rhodamine-based dye
The colored photosensitive resin composition according to the present invention contains a rhodamine-based dye in a particle state.
In one 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 1 or more of c.i. solvent red 49.
The colored photosensitive resin composition according to the present invention contains a rhodamine-based dye in a particle state, and therefore, when a color filter is produced, there is an advantage that pixels on a color filter substrate, particularly cyan pixels, have a high contrast.
Although not limited to the above theory, in a color filter substrate using a general dye, the dye is dissolved in the composition, and thus, a decrease in contrast due to dry coagulation at the time of free baking, a decrease in contrast due to oxidation of dye molecules by ultraviolet rays at the time of exposure, a decrease in contrast due to decomposition, sublimation, and the like of dye molecules at the time of post baking, and the like can occur.
However, in the present invention, since the rhodamine dye is present in a particle state, the rhodamine dye is stably maintained in a particle state even after coating, drying, exposure, development, and post-baking, and thus there is an advantage that the contrast of a pixel of a color filter, particularly a cyan pixel, is excellent.
The rhodamine-based dye may be insoluble in propylene glycol monomethyl ether acetate (PMA) as an ester-based solvent. The PMA is a solvent which has been widely used in a colored photosensitive resin composition using a pigment because it is excellent in stability, coatability, drying property, and dispersion stability of the pigment, and when the rhodamine-based dye is insoluble in the PMA, the pigment described later and the rhodamine-based dye can be stably present in the PMA in a particle state without impairing the above-described characteristics, and thus it is preferable.
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 preferably used+、Cl-、SO4 2-The sum of such ionic impurities is 20000ppm or less, more preferably 10000ppm or less. Na contained in the above rhodamine-based dye+、Cl-、SO4 2-When the sum of such ionic impurities is 20000ppm or less, the PMA can be prevented from being contaminatedA phenomenon in which dispersion stability is lowered due to ionic impurities.
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 a Particle state in the colored photosensitive resin composition can be confirmed by using a Particle size analyzer (Particle size analyzer, accusizer 780A).
In order to examine whether or not the rhodamine-based dye is in a particle state or a molecular state in a color filter produced using the colored photosensitive resin composition of the present invention, the cyan pixel of the color filter can be determined by FIB-TEM analysis and EDX elemental analysis, for example, as described below. In the color filter produced above, 100 particles of the pigment particles and the rhodamine-based dye particles were analyzed because they were mixed. 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 section was subjected to elemental analysis by EDX. When the EDX analysis results of 100 particles are compared with the EDX analysis results of the rhodamine-based dye itself, and if 1 to 100 particles having the same analysis results are present, it can be determined whether or not the rhodamine-based dye is present in a particle state 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 coating 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 diameter of the rhodamine dye exceeds 200nm, the transmittance and contrast may be slightly reduced by scattering of the particles, and when the average particle diameter of the rhodamine dye is less than 30nm, the alkali solubility of the binder resin in unexposed portions may be slightly reduced, and the pattern processability may be slightly reduced.
The average particle diameters of the rhodamine dye and the pigment can be adjusted to the above ranges by applying a shear stress to the rhodamine dye and the pigment using a dispersing machine such as a sand mill or a ball mill using zirconia beads.
However, under the dispersion conditions of the conventionally known pigments, it may be somewhat difficult to adjust the average particle diameter of the rhodamine-based dye to the above range. In short, the pigment powder has a structure in which 1-order particles of about 30nm are aggregated to form powder particles of several μm. Since the pigment powder has a small cohesive force between 1 st order particles, the pigment powder can be dispersed by dispersing 1 st order particles in a short time with a relatively weak shear stress, and can have an average particle diameter of 30 to 200 nm. However, the dye powder has a molecular set of about 1nm formed of coarse particles of several μm. Since the dye powder has a strong intermolecular cohesive force, it is slightly difficult to make the average particle diameter smaller than 200nm with a weak shear stress. In addition, since 1 st order particles are not present in the dye, if the shear stress is increased or the dispersion time is prolonged, the average particle diameter can be made smaller than 30 nm.
Therefore, in the present invention, it is preferable to disperse the rhodamine-based dye and the pigment under different dispersion conditions so that the average particle diameter of the dye and the pigment is 30 to 200 nm.
The condition for dispersing the rhodamine dye is preferably such that zirconia beads having a bead diameter of 0.3 to 2.0 μm are used and the dispersion time is 3 to 10 hours/kg with a strong shear stress, and the condition for dispersing the pigment is preferably such that zirconia beads having a bead diameter of 0.1 to 2.0 μm are used and the dispersion time is 1 to 10 hours/kg.
In the present invention, it is preferable that the rhodamine-based dye dispersion and the pigment dispersion which have undergone separate dispersion processes are mixed and then further subjected to a dispersion process. Through this process, the average particle diameters of the rhodamine-based dye and the pigment can be adjusted to a range of 30 to 100nm, and the transmittance and contrast can be further improved.
As the additional dispersion condition of the mixed dispersion, it is preferable to use zirconia beads having a bead diameter of 0.01 to 0.2 μm and to use a weak shear stress for a dispersion time of 0.1 to 3 hours/kg.
In addition, the colored photosensitive resin composition of the present invention contains both a rhodamine-based dye and a dispersant containing a triazine-based compound, which are dispersion-stabilized in the composition, and thus has an advantage that the problem of lowering the contrast can be further improved 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 rhodamine dye is contained within the above range, the dispersion stability and the transmittance are preferable. When the rhodamine dye is contained in an amount of less than 1 part by weight, the transmittance may be slightly lowered, and when the amount exceeds 80 parts by weight, the dispersion stability may be slightly lowered due to coagulation of the dye.
Dispersant containing triazine compound
The colored photosensitive resin composition according to the present invention comprises: a dispersant comprising a triazine-based compound. The triazine compound is not limited to the above-mentioned one as long as it is known as a dispersant in this field. For example, triazine dispersants described in Japanese patent application laid-open Nos. 2008-214515 and 2011-032374 can be used.
In another embodiment of the present invention, the triazine-based compound includes a compound represented by the following chemical formula 1.
[ chemical formula 1]
In the chemical formula 1, the metal oxide is represented by,
r is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a straight or branched alkoxy group having 1 to 20 carbon atoms or a group-NR 1R2,
r1 and R2 are each independently a hydrogen atom or 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 straight or branched alkoxy group having 1 to 20 carbon atoms.
In this case, examples of the alkyl group having 1 to 20 carbon atoms include a straight-chain or branched alkyl group having 1 to 20 carbon atoms such as 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.
Examples of the alkoxy group having 1 to 20 carbon atoms include straight or branched alkoxy groups having 1 to 20 carbon atoms such as 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.
The dispersant according to the present invention includes the triazine compound represented by the above chemical formula 1, and can uniformly disperse the pigment and the rhodamine dye in various media. Therefore, the colored photosensitive resin composition containing the triazine compound of the present invention has good storage stability because re-coagulation and viscosity increase of the pigment and the rhodamine dye are suppressed.
In addition, when the triazine compound is used in combination with a resin-type dispersant in a dispersant, the effect of improving the dispersibility of the pigment and the rhodamine-based dye and the effect of suppressing reagglomeration can be particularly remarkable.
In addition, the triazine compound represented by the above chemical formula 1 of the present invention shows white in the visible region, and therefore, a color liquid crystal display capable of high-luminance color development can be manufactured using a color filter formed from a colored photosensitive resin composition containing the above triazine compound. The triazine compound has a relatively low initial viscosity and a high effect of inhibiting the re-coagulation of the pigment, and therefore has the characteristics of excellent storage stability of the dispersant and a relatively small increase in viscosity due to storage.
In another embodiment of the present invention, 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 total colorant. When the triazine compound is contained in the above range, crystal growth of the rhodamine dye and the pigment can be suppressed, and therefore, this is preferable. When the triazine compound is contained in an amount of less than 0.1 part by weight based on the colorant, the rhodamine dye may aggregate, and when the amount is more than 60 parts by weight, the contrast may be slightly lowered.
Coloring agent
The colorant of the present invention may contain 1 or more kinds of the above rhodamine-based dye, 1 or more kinds of the pigment and the above pigment dispersant. The above-mentioned rhodamine-based dyes can be applied.
The pigment may be an organic pigment or an inorganic pigment generally used in this field. As the pigment, various pigments used in printing inks, inkjet inks, and the like can be used, and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, peryleneketone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinone pigments, anthrapyrimidine pigments, anthrone (anthanthrone) pigments, indanthrone (indanthrone) pigments, xanthone pigments, pyranthrone (pyranthrone) pigments, and diketopyrrolopyrrole pigments.
Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically include metal oxides or composite metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black. In particular, as The organic pigment and The inorganic pigment, specifically, compounds classified as pigments in The color index (published by The society of Dyers and Colourists) are listed, more specifically, pigments in The following color index (c.i.) numbers are listed, but not necessarily limited thereto.
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 and 185
C.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71
C.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264
C.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38
C.i. pigment blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76
C.i. pigment green 7, 10, 15, 25, 36, 47, 58, 59, 62 and 63
C.i. pigment brown 28
C.I. pigment Black 1 and 7, etc
The above pigments can be used each alone or in combination of 2 or more.
Among the above exemplified c.i. pigments, those 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. c.i. pigment blue 15: 6.
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 size of the pigment include a method of dispersing the pigment with a pigment dispersant, and this method is preferable because a colorant dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.
The pigment dispersant may be further added to the triazine compound-containing dispersant, and examples thereof include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and other surfactants, and these may be used alone or in combination of 2 or more types, but are not limited thereto.
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 whole colorant dispersion. The content of the pigment is preferably in the range of 1 to 50 parts by weight based on the above-mentioned reference because the viscosity is low, the storage stability is excellent, the dispersion efficiency is high, and the increase of the contrast ratio is effective.
The colorant dispersion liquid may further contain a dispersion medium.
The dispersion medium is added to maintain the deagglomeration and stability of the pigment, and a dispersion medium generally used in this field can be used without limitation. It may preferably contain an acrylate-based dispersant (hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). In this case, it is preferable to use a dispersant manufactured by an activity control method proposed in Korean laid-open patent No. 2004-0014311 as the acrylic dispersant, and examples of commercially available acrylate 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 2 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, oily dispersants such as polyurethanes, polycarboxylates typified 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 imines); 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; ethylene oxide/propylene oxide addition products, phosphoric esters, and the like. As a commercial product of the above resin type dispersant, a cationic resin dispersant includes, for example, a trade name of BYK (ビック) chemical: 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 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 corporation: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Chuanjia fine chemical company: ヒノアクト (HINACT) T-6000, ヒノアクト T-7000, ヒノアクト T-8000; trade name of Aomoto Co., Ltd: アジスパー (AJISPUR) PB-821, アジスパー PB-822, アジスパー PB-823; trade name of Kyoeisha chemical Co., Ltd: フローレン (FLORENE) DOPA-17HF, フローレン DOPA-15BHF, フローレン DOPA-33, フローレン DOPA-44, etc. In addition to the above-mentioned acrylic dispersants, other resin-type pigment dispersants may be used alone or in combination of 2 or more types, or may be used in combination with the acrylic dispersant.
The pigment dispersant may be contained in an amount of 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.
In another embodiment of the present invention, the colored photosensitive resin composition may further comprise at least one selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent.
Alkali soluble resin
The alkali-soluble resin is polymerized from ethylenically unsaturated monomers having carboxyl groups. This is a component that imparts solubility to an alkali developer used in a developing process step 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 and methacrylic acid. These may be used alone or in combination of 2 or more.
The alkali-soluble resin according to the present invention may be a product obtained by polymerizing at least 1 monomer copolymerizable with the above-mentioned monomer. Examples thereof include 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. These may be used alone or in combination of 2 or more.
In the present specification, (meth) acrylate means acrylate or methacrylate.
The content of the alkali-soluble resin according to the present invention is not particularly limited, and is, for example, preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, based on 100 parts 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, so that the pattern formation is easy, the film of the pixel portion at the exposure portion is prevented from being reduced during the development, and the releasability of the non-pixel portion can be improved.
Photopolymerizable compound
The photopolymerizable compound contained in the colored photosensitive resin composition of the invention is a compound polymerizable by light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, 2-functional monomers, and other polyfunctional monomers.
The monofunctional monomer is not particularly limited in kind, and examples thereof include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.
The type of the 2-functional monomer is not particularly limited, and examples thereof include 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, 3-methylpentanediol di (meth) acrylate, and the like.
The type of the polyfunctional monomer is not particularly limited, and examples thereof include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
The photopolymerizable compound is preferably contained in an amount of 5 to 50 parts by weight, more preferably 7 to 48 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. If the content of the photopolymerizable compound is within the above range, the strength and smoothness of the pixel portion can be improved.
Photopolymerization initiator
The photopolymerization initiator contained in the colored photosensitive resin composition of the present invention is not limited, and is 1 or more compounds selected from triazine compounds, acetophenone compounds, bisimidazole compounds, and oxime compounds. The photosensitive resin composition containing the photopolymerization initiator has high sensitivity, and the strength and the pattern of a pixel (pixel) formed using the composition are improved.
Further, if a photopolymerization initiator and a photopolymerization initiation auxiliary are used in combination, a photosensitive resin composition containing these is further highly sensitive, and productivity in forming a color filter using the composition is improved, which is preferable.
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, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl ] -1,3, 5-triazine A group ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and the like.
Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, oligomers of 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, and the like.
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 by an alkoxycarbonyl group. Among these, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole and 2,2' -bis (2, 3-dichlorophenyl) -4, 4', 5, 5' -tetraphenylbiimidazole are preferably used.
In addition, other photopolymerization initiators and the like generally used in the field may be further included to the extent that the effects of the present invention are not impaired. Examples of the other photopolymerization initiator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and anthracene compounds. These can be used each alone or in combination of 2 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 O-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 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.
Examples of the other photopolymerization initiator include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9, 10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compound.
In the present invention, as the photopolymerization initiation auxiliary agent which can be used in combination with the photopolymerization initiator, 1 or more compounds selected from amine compounds, carboxylic acid compounds, and the like can be preferably used.
Specific examples of the amine compound in the photopolymerization initiation assistant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, and the like, and 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 (known as Michler's ketone), 4' -bis (diethylamino) benzophenone, and the like. As the amine compound, an aromatic amine compound is preferably used.
Examples of the carboxylic acid compound include aromatic heteroacetic acids 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 in the colored photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 1 to 12 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. When the amount of the photopolymerization initiator is within the above range, the photosensitive resin composition has high sensitivity, and the strength of the pixel portion and the smoothness of the surface of the pixel portion are excellent.
The amount of the photopolymerization initiation assistant used is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. When the amount of the photopolymerization initiation auxiliary is within the above range, the sensitivity efficiency of the photosensitive resin composition is further improved, and the productivity of a color filter formed using the composition can be improved.
Solvent(s)
The solvent contained in the colored photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of colored photosensitive resin compositions 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 methoxyamyl 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.
The solvent is preferably an organic solvent having a boiling point of 100 to 200 ℃ among the solvents in terms of coatability and drying property, more preferably an ester such as alkylene glycol alkyl ether acetate, a ketone, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate, and further preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate. These solvents can be used each alone or in combination of 2 or more.
The content of the solvent in the colored photosensitive resin composition of the present invention is preferably 60 to 90 parts by weight, more preferably 68 to 85 parts by weight, based on 100 parts by weight of the entire photosensitive resin composition containing the solvent. When the content of the solvent is within the above range, the coating properties can be improved when the coating is performed by a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an inkjet.
The colored photosensitive resin composition according to the present invention may further contain other additives such as a polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-coagulation agent, and the additives may be appropriately added and used by those skilled in the art within a range not to impair the effects of the present invention.
< color filter >
Another embodiment of the present invention relates to a color filter produced using the colored photosensitive resin composition.
The color filter includes a substrate and a pattern layer formed on the substrate.
The substrate may be a substrate of the color filter itself, or may be a portion where the color filter is located in a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyether sulfone (PES), Polycarbonate (PC), or the like.
The pattern layer is a layer containing the colored photosensitive resin composition of the present invention, and may be a layer formed by applying the colored photosensitive resin composition, exposing to light in a predetermined pattern, developing, and thermally curing. The above-described pattern layer can be formed by performing a method generally known to those skilled in the art.
The color filter including the substrate and the pattern layer may further include a partition wall formed between the patterns, and may further include a black matrix, but is not limited thereto.
In addition, the protective film may further include a protective film formed on the color filter pattern layer.
< image display device >
Another embodiment of the present invention relates to an image display device including the color filter.
The color filter of the present invention is applicable not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.
The image display device of the present invention has excellent light efficiency, high display luminance, excellent color reproducibility, and high contrast.
The present invention will be described in detail below with reference to examples. However, the embodiments described in the present specification can be modified into various other forms, and the scope of the present specification should not be construed as being limited to the embodiments described in detail below. The embodiments of the present disclosure are provided to more fully explain the present disclosure to those skilled in the art. The following "%" and "part(s)" of the content are based on weight unless otherwise specified.
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 resulting reaction mass was allowed to react at 85 ℃ for 5 hours. The residue obtained by leaching the obtained reactant was washed with water and then left to stand overnight in a thermostatic bath at 100 ℃ to be dried, whereby a compound of the following chemical formula 2 was obtained.
[ chemical formula 2]
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 obtained reaction product was leached out to obtain a residue, which was washed with water, and then left to stand overnight in a thermostatic bath at 100 ℃ and dried to obtain a compound of the following chemical formula 3.
[ chemical formula 3]
Synthesis example 3: triazine Compound 3
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 1, 3-butanediol, 10 parts by weight of sodium hydroxide was added, and then the mixture was reacted at 10 ℃ for 3 hours. The resulting reaction mass was allowed to react at 85 ℃ for 5 hours. The obtained reaction product was leached out to obtain a residue, which was washed with water, and then left to stand overnight in a constant temperature bath at 100 ℃ and dried to obtain a compound of the following chemical formula 4.
[ chemical formula 4]
Resin (B-1)
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared, while 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) were charged as a monomer dropping funnel, and then stirred and mixed to prepare a chain transfer agent dropping tank, in which 6g of n-dodecanethiol and 24g of PGMEA were charged and stirred and mixed. Then, 395g of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen gas from the air, and the temperature of the flask was raised to 90 ℃ with stirring. Next, the monomer and the chain transfer agent were dropped from the dropping funnel. Dropping was carried out for 2 hours while maintaining 90 ℃,1 hour later, the temperature was raised to 110 ℃, and after maintaining for 3 hours, the gas introduction tube was introduced, and bubbling of a mixed gas of 5/95(v/v) with oxygen/nitrogen was started. Then, 28.4g of glycidyl methacrylate [ (0.10 mol), (33 mol% based on the carboxyl group of acrylic acid used in the reaction) ], 0.4g of 2,2' -methylenebis (4-methyl-6-tert-butylphenol), and 0.8g of triethylamine were put into a flask, and the reaction was continued at 110 ℃ for 8 hours to obtain a resin B-1 having a solid acid value of 70 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 16000, and the molecular weight distribution (Mw/Mn) was 2.3.
Resin (B-2)
182g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, the atmosphere in the flask was replaced with nitrogen gas from the air, the temperature was raised to 100 ℃, and then a solution prepared by adding 3.6g of azobisisobutyronitrile to a mixture comprising 70.5g (0.40 mol) of benzyl methacrylate, 45.0g (0.50 mol) of methacrylic acid, 22.0g (0.10 mol) of 2- (2-methyl) adamantane ester methacrylate and 136g of propylene glycol monomethyl ether acetate was dropped into the flask from the dropping funnel over 2 hours, and stirring was continued at 100 ℃ for a further 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 30g of glycidyl methacrylate [0.2 mol (% 40 mol based on the carboxyl group of methacrylic acid used in the reaction) ], 0.9g of tris (dimethylaminomethyl) phenol and 0.145g of hydroquinone were placed in the flask, and the reaction was continued at 110 ℃ for 6 hours to obtain resin B-2 having a solid acid value of 99 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 23000, and the molecular weight distribution (Mw/Mn) was 2.3.
The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin was performed 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: 1.0 ml/min
Injection amount: 50 μ l
A detector: RI (Ri)
And (3) measuring the concentration of the sample: 0.6% by mass (solvent ═ tetrahydrofuran)
Calibration standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)
The ratio of the weight average molecular weight to the number average molecular weight obtained above was taken as the molecular weight distribution (Mw/Mn).
Preparation of colorant Dispersion 1
20.48 parts by weight of the compound of chemical formula 2 of synthesis example 1 as a triazine derivative, c.i. pigment blue 15: 69.12 parts by weight, C.I. acid Red 522.88 parts by weight, acrylic dispersant [ Disperbyk (registered trademark) 2000; ビック ケ ミ ー Inc. ]3.84 parts by weight, 12.88 parts by weight of a resin B, 55.04 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 5.76 parts by weight of propylene glycol monomethyl ether, and 360 parts by weight of zirconia beads having a diameter of 0.2mm were put into a mayonnaise bottle having a capacity of 140ml, kneaded at 60 ℃ for 10 hours using a paint conditioner, and then dispersed. Then, the zirconia beads 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.
Preparation of colorant Dispersion 2
The preparation of the colorant dispersion liquid 1 was performed in the same manner as in synthesis example 2 except that the compound of chemical formula 3 was used as the triazine derivative.
Preparation of colorant Dispersion 3
The preparation of the colorant dispersion liquid 1 was performed in the same manner as in synthesis example 3, except that the compound of chemical formula 4 was used as the triazine derivative.
Preparation of colorant Dispersion 4
The same procedure as in the preparation of the colorant dispersion liquid 1 was carried out except that the triazine derivative was not used.
Preparation of colorant Dispersion 5
The procedure was carried out in the same manner as in the preparation of the colorant dispersion liquid 1, except that rhodamine B was used as the rhodamine-based dye.
Production of colored photosensitive resin composition
Colored photosensitive resin compositions according to examples and comparative examples were produced according to the compositions described in table 1 below.
[ TABLE 1]
Example of production of color Filter (glass substrate)
Color filters were produced using the colored photosensitive resin compositions produced in examples and comparative examples. That is, after each of the colored photosensitive resin compositions was applied onto a glass substrate by a spin coating method, the glass substrate was placed on a hot plate and maintained at a temperature of 100 ℃ for 3 minutes to form a thin film. Next, placing the film on the film to make the transmittance of the filmThe test photomask having a pattern varying stepwise in the range of 1 to 100% and a line/space pattern of 1 to 50 μm was irradiated with ultraviolet rays with a spacing of 100 μm from the test photomask. In this case, a 1kW high-pressure mercury lamp containing the entire g, h and i lines was used as the ultraviolet light source at a rate of 100mJ/Cm2The illumination of (2) is performed without using a special optical filter. The film subjected to the ultraviolet irradiation was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes to be developed. The glass plate to which the thin film was applied was washed with distilled water, then dried by spraying nitrogen gas, and heated in a heating oven at 220 ℃ for 1 hour to produce a color filter. The film thickness of the color filter produced above was 2.0. mu.m.
Determination of contrast
The contrast of the colored glass plates (color filters) after post-baking of examples 1 to 3 and comparative examples 1 and 2 was measured using a contrast measuring apparatus.
The contrast measuring apparatus was composed of a color luminance meter (trade name: LS-100 manufactured by コニカミノルタセンシング Co., Ltd.), a lamp (trade name: HF-SL-100WLCG manufactured by ジョントン industries Co., Ltd.) and a polarizing plate (trade name: POLAX-38S manufactured by ルケオ Co., Ltd.).
A polarizing plate (POLAX-38S) was provided on the backlight so that the distance between the polarizing plate and the colored glass plate became 1 mm.
A rotatable polarizing plate is provided at an upper portion thereof. After confirming that the luminance of the backlight was sufficiently stabilized, the rotatable polarizing plate provided at the upper portion was adjusted to a position orthogonal to nicols, and the luminance of the colored glass plate was measured, and then rotated by 90 degrees, and the luminance of the colored glass plate was measured at a parallel position. The ratio (%) of the two was obtained as the contrast.
The results are shown in the following table 2, and the contrast values of examples 1 to 3 are relative values when the contrast of a colored glass plate obtained using the colored photosensitive resin composition of comparative example 1 is taken as a standard (100).
Measurement of luminance (Y)
The brightness (Y) of the colored glass sheets according to examples 1 to 3 and comparative examples 1 and 2 was measured as follows. The colored glass plate was set to a spectrocolorimeter (trade name: CM-3700d, manufactured by コニカミノルタセンシング corporation), and the transmission chromaticity was measured in the X, Y, Z coordinate axis at 2 degrees (°) from a C light source. The value Y at this time is used as the luminance (Y). The results are shown in table 2 below.
The brightness values of examples 1 to 3 in table 2 below are relative values when the brightness of a colored glass plate obtained using the colored photosensitive resin composition of comparative example 1 is defined as a standard (100).
Measurement of development residue
The presence or absence of residues on the colored glass plates of examples 1 to 3 and comparative examples 1 and 2 was confirmed by an optical microscope. The results are shown in table 2 below, and the results of the development residue are indicated as "o" when no residue is present and as "x" when a residue is present.
Measurement of Heat resistance
The colored glass plates (color filters) after post-baking of examples 1 to 3 and comparative examples 1 and 2 were compared and evaluated for color change at a temperature of 230 ℃ for 2hr (hours). The colored glass plate was set on a spectrophotometer (trade name: CM-3700d, manufactured by コニカミノルタセンシング corporation), and the L-, a-, and b-fold values at 2 degrees (at) from the C light source were measured. The color change using a 3-dimensional colorimeter defined as L, a, and b is calculated according to the following equation 1, and the smaller the color change value is, the more reliable a color filter can be manufactured.
[ mathematical formula 1]
△Eab＊＝[(△L＊)2+(△a＊)2+(△b＊)2]1/2
In Table 2 below, the brightness values of examples 1 to 3 are relative values when the heat resistance of a colored glass plate obtained by using the colored photosensitive resin composition of comparative example 1 is defined as a standard (100).
Determination of solvent resistance
The colored glass plates (color filters) after post-baking of examples 1 to 3 and comparative examples 1 and 2 were immersed in an N-methylpyrrolidone solvent for 30 minutes, and the color change before and after the evaluation was compared and evaluated. The colored glass plate was set in a spectrophotometer (trade name: CM-3700d, manufactured by コニカミノルタセンシング K.) and the L-, a-, b-values at 2 degrees (at) of C illuminant were measured. The color change using a 3-dimensional colorimeter defined as L, a, and b is calculated according to the above [ equation 1], and the smaller the color change value is, the more reliable color filter can be manufactured.
In Table 2 below, the brightness values for examples 1-3 are shown: the solvent resistance of the colored glass plate obtained by using the colored photosensitive resin composition of comparative example 1 was defined as a relative value in the case of the standard (100).
[ TABLE 2]
| Brightness of light | Contrast ratio | Development residue | Heat resistance | Solvent resistance | |
| Example 1 | 1.05 | 3.14 | ○ | 1.05 | 1.08 |
| Example 2 | 1.07 | 3.21 | ○ | 1.03 | 1.02 |
| Example 3 | 1.06 | 3.65 | ○ | 1.07 | 1.01 |
| Comparative example 1 | 1.00 | 1.00 | ○ | 1.00 | 1.00 |
| Comparative example 2 | 1.09 | 10.27 | × | 0.24 | 0.17 |
In the case of examples 1 to 3 using triazine of the structure of chemical formula 1, high contrast was obtained similarly to comparative example 1 in terms of brightness, development residue, heat resistance, and solvent resistance without adding a triazine derivative, and good development residue and high heat resistance and solvent resistance were obtained similarly to comparative example 2 in terms of brightness using a soluble rhodamine-based dye.
Claims (6)
1. A colored photosensitive resin composition comprising:
a colorant comprising a rhodamine-based dye and a pigment in a particle state; and
a dispersant comprising a triazine-based compound, a dispersant,
wherein the triazine-based compound includes a compound represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the metal oxide is represented by,
r is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a straight or branched alkoxy group having 1 to 20 carbon atoms or a group-NR 1R2,
r1 and R2 are each independently a hydrogen atom or 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 straight or branched alkoxy group having 1 to 20 carbon atoms.
2. 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 1 or more of c.i. solvent red 49.
3. The colored photosensitive resin composition according to claim 1, wherein the triazine compound is contained in an amount of 0.1 to 60 parts by weight based on 100 parts by weight of the total colorant.
4. The colored photosensitive resin composition according to claim 1, further comprising at least one selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent.
5. A color filter produced using the colored photosensitive resin composition according to any one of claims 1 to 4.
6. An image display device comprising the color filter according to claim 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160036568A KR102383698B1 (en) | 2016-03-28 | 2016-03-28 | Colored photosensitive resin composition, color filter and image display device produced using the same |
| KR10-2016-0036568 | 2016-03-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107239004A CN107239004A (en) | 2017-10-10 |
| CN107239004B true CN107239004B (en) | 2021-07-13 |
Family
ID=59982976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710016692.2A Active CN107239004B (en) | 2016-03-28 | 2017-01-10 | Colored photosensitive resin composition, color filter and image display device manufactured using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6654556B2 (en) |
| KR (1) | KR102383698B1 (en) |
| CN (1) | CN107239004B (en) |
| TW (1) | TWI685713B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021162854A (en) * | 2020-03-31 | 2021-10-11 | 住友化学株式会社 | Negative resist composition |
| CN113201017B (en) * | 2021-04-29 | 2022-07-01 | 宁波中苑颜料有限公司 | Organic pigment dispersant based on triazine derivative and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1977221A (en) * | 2004-05-31 | 2007-06-06 | 富士胶片株式会社 | Pattern forming method, color filter manufacturing method, color filter, and liquid crystal display |
| KR20120020482A (en) * | 2010-08-30 | 2012-03-08 | 주식회사 알파켐 | Pigment dispersion composition, color resist, and color filter |
| JP2012194523A (en) * | 2011-02-28 | 2012-10-11 | Toyo Ink Sc Holdings Co Ltd | Coloring composition for color filter, and color filter |
| JP2012233034A (en) * | 2011-04-28 | 2012-11-29 | Dainippon Printing Co Ltd | Dye dispersion, photosensitive resin composition for color filter, color filter, liquid crystal display device, and organic light-emitting display device |
| JP2012246393A (en) * | 2011-05-27 | 2012-12-13 | Dainippon Printing Co Ltd | Pigment dispersant, pigment dispersion, colored resin composition for color filter, color filter, liquid crystal display device and organic light emitting display device |
| JP2013041145A (en) * | 2011-08-17 | 2013-02-28 | Toyo Ink Sc Holdings Co Ltd | Coloring composition for color filter, and color filter |
| JP2013061619A (en) * | 2011-08-24 | 2013-04-04 | Toray Ind Inc | Blue colorant composition for color filter and color filter substrate using the same |
| JP2013101166A (en) * | 2011-10-12 | 2013-05-23 | Toyo Ink Sc Holdings Co Ltd | Colored composition for color filter, and color filter |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5353519B2 (en) * | 2009-07-21 | 2013-11-27 | Ｊｓｒ株式会社 | Coloring composition, color filter and color liquid crystal display element |
| WO2011065228A1 (en) * | 2009-11-30 | 2011-06-03 | 株式会社タムラ製作所 | Curable composition, cured material therefrom, and use thereof |
| JP6192968B2 (en) * | 2012-04-10 | 2017-09-06 | 住友化学株式会社 | Colorant dispersion |
| KR102116438B1 (en) * | 2012-05-21 | 2020-05-29 | 토요잉크Sc홀딩스주식회사 | Colored composition for color filter and color filter |
| CN104428331B (en) * | 2012-07-11 | 2019-02-15 | 东洋油墨Sc控股株式会社 | Active energy beam polymer resin composition and the laminated body for using the resin combination |
| KR20140112228A (en) * | 2013-03-13 | 2014-09-23 | 동우 화인켐 주식회사 | Colored photosensitive resin composition and color filter |
| TWI641657B (en) * | 2013-10-03 | 2018-11-21 | 南韓商東友精細化工有限公司 | Dye dispersion |
| TWI547486B (en) * | 2013-12-12 | 2016-09-01 | 中央研究院 | Compounds and methods for analysis and synthesis of saccharide compounds |
| WO2016006738A1 (en) * | 2014-07-10 | 2016-01-14 | 전북대학교산학협력단 | Inducer for vertically aligning liquid crystals and liquid crystal display device manufactured using same |
-
2016
- 2016-03-28 KR KR1020160036568A patent/KR102383698B1/en active IP Right Grant
- 2016-11-30 TW TW105139404A patent/TWI685713B/en active
- 2016-12-27 JP JP2016252876A patent/JP6654556B2/en active Active
-
2017
- 2017-01-10 CN CN201710016692.2A patent/CN107239004B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1977221A (en) * | 2004-05-31 | 2007-06-06 | 富士胶片株式会社 | Pattern forming method, color filter manufacturing method, color filter, and liquid crystal display |
| KR20120020482A (en) * | 2010-08-30 | 2012-03-08 | 주식회사 알파켐 | Pigment dispersion composition, color resist, and color filter |
| JP2012194523A (en) * | 2011-02-28 | 2012-10-11 | Toyo Ink Sc Holdings Co Ltd | Coloring composition for color filter, and color filter |
| JP2012233034A (en) * | 2011-04-28 | 2012-11-29 | Dainippon Printing Co Ltd | Dye dispersion, photosensitive resin composition for color filter, color filter, liquid crystal display device, and organic light-emitting display device |
| JP2012246393A (en) * | 2011-05-27 | 2012-12-13 | Dainippon Printing Co Ltd | Pigment dispersant, pigment dispersion, colored resin composition for color filter, color filter, liquid crystal display device and organic light emitting display device |
| JP2013041145A (en) * | 2011-08-17 | 2013-02-28 | Toyo Ink Sc Holdings Co Ltd | Coloring composition for color filter, and color filter |
| JP2013061619A (en) * | 2011-08-24 | 2013-04-04 | Toray Ind Inc | Blue colorant composition for color filter and color filter substrate using the same |
| JP2013101166A (en) * | 2011-10-12 | 2013-05-23 | Toyo Ink Sc Holdings Co Ltd | Colored composition for color filter, and color filter |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170111323A (en) | 2017-10-12 |
| TWI685713B (en) | 2020-02-21 |
| JP6654556B2 (en) | 2020-02-26 |
| JP2017182044A (en) | 2017-10-05 |
| TW201802585A (en) | 2018-01-16 |
| KR102383698B1 (en) | 2022-04-05 |
| CN107239004A (en) | 2017-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111399340B (en) | Colored photosensitive resin composition, color filter comprising same, and display device | |
| CN105974739B (en) | Colored photosensitive resin composition, color filter and liquid crystal display device | |
| CN108345174B (en) | Colored photosensitive resin composition, color filter and image display device | |
| KR20160109834A (en) | Colored photosensitive resin composition | |
| TWI485515B (en) | Colored photosensitive resin composition and color filter using the same | |
| CN107239004B (en) | Colored photosensitive resin composition, color filter and image display device manufactured using the same | |
| CN107783372B (en) | Colored photosensitive resin composition, color filter, and image display device provided with same | |
| CN108073040B (en) | Colored photosensitive resin composition, color filter and image display device manufactured by using same | |
| KR101992867B1 (en) | Colored photosensitive resin composition | |
| CN108333867B (en) | Colored photosensitive resin composition, color filter and image display device | |
| CN107976865B (en) | Colored photosensitive resin composition, color filter and image display device manufactured by using same | |
| CN108375875B (en) | Colored photosensitive resin composition, color filter and image display device | |
| KR20140014622A (en) | A colored photosensitive resin composition | |
| CN110045576B (en) | Colored photosensitive resin composition, color filter comprising same, and image display device | |
| CN108398855B (en) | Green photosensitive resin composition, color filter and image display device | |
| KR20110030084A (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| CN108375876B (en) | Colored photosensitive resin composition, color filter and image display device | |
| KR101987657B1 (en) | Colored photosensitive resin composition | |
| CN106019843B (en) | Colored photosensitive resin composition and color filter manufactured by same | |
| KR101475070B1 (en) | Colored photosensitive resin composition, color filter, and liquid crystal display device having the same | |
| KR20170097403A (en) | Triazine compound, pigment dispersant, pigment composition, self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same | |
| CN111679557A (en) | Colored curable resin composition containing blue dye, color filter, and image display device | |
| KR20200114021A (en) | A colored photo sensitive resin composition, a color filter comprising the same, and an image display devide comprising the color filter | |
| KR20170014507A (en) | Laminated substrate having colored photosensitive resin layer and silica doped base material | |
| KR20140087983A (en) | Colored photosensitive resin composition and color filter using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |